Inhaltsverzeichnis. Contents. -Table des...

Inhaltsverzeichnis.

Contents. -Table des matieres.

The Biosynthesis of Rubber. By JAMES BONNER, California Institute of

Technologie, Pasadena, California I

L Distribution of Rubber I

II. Latex. 2

Structure and Configuration 2

III. Biogenesis of the Monomer 4

IV. Polymerization V. Further Problems. References. The Polyene Antifungal Antibiotics. By W. OROSHNIK, Central Research

Laboratory Shulton, Clifton, New Jersey, and A. D. MEBANE, Ortho

Research Foundation, Raritan, New Jersey. I. Introduction. II. Ultraviolet Spectra. I. General Observations 2. The Tetraenes. 3. The Pentaenes 4. The Methylpentaenes 5. The Hexaenes 6. The Heptaenes III. Structural Elucidation I. General Features 2. Mycosamine. 3. Retro-Aldol Cleavage. 4. Fungichromin (Lagosin) 5. Filipin 6. Other Methylpentaenes. 7. Pimaricin 8. Nystatin and Other Tetraenes 9. Pentaenes and Hexaenes 10. Trichomycin and Other Heptaenes IV. Biogenetic Relationships V. Tables I. TypicalTetraenes: Spectralbata ,

2. TypicalPentaenes: Spectral Data 3. Typical Methylpentaenes: Spectral Data. 4. TypicalHexaenes: Spectral Data ". TVpicalHeptaenes: Spectral Data

13

18

19

192324242424

26

2628

3032373940434546

51

56

5656575757

IV

5862

6466

66

'72

6. Tetraenes: Physical and Chemical Properties. 7. Pentaenes: Physical aIid ChemicalProperties 8. Methylpentaenes.: Physical an~ Chemical ~opertie,. 9. Hexaenes: Physlcal. and Chemlcal Propertles ,. 10. Heptaenes: Physical and Chemical Properties. References ,..., , Die Chemie der Tetracycline. Voti H. MUXFELDT und R. BANGERT,

Department of Chemistry, The University of Wisconsin, Madison,

Wisconsin 8°

I. Einleitung 80

II. Konstitutionsatifklarung 82

I. Terramycin 82

Alkalischer Abbau 83

Saurer Abbau 87

Reduktiver Abbau 90

2. Aureomycin 91

3. 6-Desmethyl-tetracycline , 96:

4. 5a,1 I a-Dehydro-7-chlor-tetracyclin 9~

5. 2-Acetyl-2-descarboxamido-tetracycline. 9i

Ip. Weitere chetnische Eigenschaften 98

I. Reaktionen am C(2) : 99

2. Reaktionen am C(4) 100

3. Reaktionenam C(6) 10Z

4. Reaktionen am C(lla) und C(12a) 108

IV. Biogenese der Tetracycline 113

V. Versuche zur Synthese von Tetracyclinen 115

Literaturverzeichnis 116

Anthracyclinone und Antht:acycline (Rhodomycinone, Pyrromycinone

und ihre Glykoside). Von HANS BROCKMANN, Organisch-chemisches

Institut der Universitat Gottingen , I. Einleitung II. Isolierung der Anthracyclinone und Anthracycline. ; I. Gewinnung der E-Pyrromycinon-glykoside und Pyrromycinone Cinerubin A und B pyrromycin und Pyrromycinone 2. Gewinnung der Rhodomycinone. Iso-rhodomycinone und ihrer

Glykoside Trennung von Rhodomycinon/Iso-rhodomycinon-Gemischen Trennung von Rhodomycinen und Iso-rhodomycinen. III. Die Anthracyclinone. I. Vorbemerkungenzur Struktur der Anthracyclinone. 2. Zur Konstitutionsermittlung der Anthracyclinone Die Aufklarung des Chromophors Die Anellierung des alityclischen Ringes

121

122

123

124

124-124

125

126

T"..

127

127

13°131133

v-Contents. Table des matieres.--Inhaltsverzeichnis.

137

13713713914°

14°14°141141145145

146146151151

154154154

155

160

163

17°

171171173173

174174175176

176176177177

178179

179179

179

Die Substituenten an RingA Schreibweise und Bezifferung der Anthracyclinon':-Formeln

3. Konstitution der Anthracyclinone ,. ..

A. Iso-rhodo~ycinone. :'

E-Iso-rhodomycinon. "r.-Iso-rhodomycinon. fJ-Iso-rhodomycinon '...

B. Rhodomycinone E-Rhodomycinon -r;-Rhodomycinon p-Rhodomycinon y-Rhodomycinon o-Rhodomycinon C. pyrromycinone 'I'J-Pyrromycinon E-PYrromycinon "r.-Pyrromycinon D. AklavinQne Aklavinon 7-Desoxy-aklavinon 4. Die KMR-Spektren der Anthracyclinone 5. Zur Stereochemie der Anthracyclinone; 6. Zur Biogenese der Anthracyclinone. IV. Die Anthracycline. I. Die Zucker der Anthracycline Rhodosamin 2-Desoxy-L-fucose Rhodinose 2. Anthracycline des E-PYrromycinons. Pyrromycin : Cinerubine Rutil~ntine 3. Anthracycline der Rhodomycinone Rhodomycin A ; Rhodomycin B y-Rhodomycine.: Tho-rhodomycinA Antibiotica. der Mycetin-Violarin-Gruppe ,

4. Anthracycline des Aklavinons Aklavin Literaturverzeichnis

183

184

187

187

Folsaure und Folat-Enzyme. Von L. ]AENICKE und C. KUTZBACH,Physiologisch-chemisches Instiut der Universitat Koln I. Einleitung II. Das Vitamin Folsaure I. Entdeckung der Folsaure und ihrer Konjugate

2. Konjugat-spaltende Enzyme 190

3. Vorkommen. Bedarf und Ausscheidung 190

III. Auf- und Abbau der Folsa.ure-Cofaktoren 192

I. Biogenese der Folsa.ure 192

2. Biologischer Abbau der Folsa.ure , 195

3. Enzymatische Reduktion der F01sa.ure zum Cofaktor 197

IV. Chemie der Folat-Verbindungen 199

I. Folsa.ure 199a. Isolierung 199b. Konstitution und physikalische Eigenschaften 200C. Chemische Eigenschaften 201

d. Folsa.ure-Synthesen 203

2. Reduktion von Folsa.ure 204a. Dihydrofolsa.ure und das Problem der Dihydrofolat-Isomerie 204

b. 5.6.7.8-Tetrahydro-folsaure 207

3.. Mit Einkohlenstoff-Korpern substituierte Folsa.uren. 209

a. 10-Formyl-folsa.ure 209b. 10-Formyl-tetrahydrofolsa.ure , 209c. 5-Formyl-tetrahydrofolsaure 211d. 5,10-Methinyl-tetrahydrofolsaure 212

e. 5-Formimino-tetrahydrofolsaure 215f. 5.10-Methylen-tetrahydrofolsaure :. 216

g. 5-Methyl-tetrahydrofolsaure 219

4. Folsa.ure-Analoge. 220

5. SpektrenvonFolat-Verbindungen 222

6. Analyse und Trennung von Folsa.ure-Verbindungen. 225a. Chemische Verfahren 225b. Polarographie ..: 225C. Mikrobiologische Methoden 226

d. Chromatographische Trennung 227

V. Das Einkohlenstoff-Reservoir 229I. Herkunft der Ameisensaure 2292. Glycin als Quelle von Einkohlenstoffkorpern. 2313. Der Einkohlenstoff-Donator Serin 2324. Herkunft der Methylgruppe 233

VI. Folat-katalysierte Enzym-Reaktionen 236

1. Der Transhydroxymethylierungs-Cyclus. 236a. Serin-Aldolase. 236b. Transhydroxymethylierungs-Reaktionen. 239c. Methylentetrahydrofolat-Dehydrogenase. 239

2. Methylengruppen-Genese , 240

a. Thymidylat-Bildung 240b. Methylentetrahydrofolat-Reduktase : 5-Methyl-tetrahydrofolsa.ure. .242c. Methionin-Bildung 243

(X. Die Gesamt-Reaktion 243p. Zusammenha.nge zwischen Folsa.ure und Vitamin B12. 244V. Der Acceptor der MethylRTuppe 245

..

~ Table des matieres. VIIContents.T nha.ltsverzeichnis.

246246247248~.Q

3. Transformylierungs-Cyclen a. Abbau von Histidin b. Deacylase und Glutamyl- Transferase. c. Aktivierte Ameisensa.ure im Purin-Stoffwechsel

(X. Verga.rung von Purinen .B. Tetrahydrofolat-Formylase. y. Transformylierungen Zusammenfassung ,~"t,,~v,,'.zeichnis

275

275

278

278

279

279

284

290

290

294

295

295

296

297298

299

301

302

3°3304

304

305

309

316

316

Chemistry of the Natural Rotenoids. By L. CROMBIE, Department of

Chemistry, University of London King.s College, Lond?n I. Introduction. II. General Remarks on Rotenone and the Rotenoids.. I. Isolation. 2. Colour Tests 3. Nomenclature. III. Stereochemistry of Rotenone .0 IV. Chemistry of Rotenone V. The Rotenolones and Isorotenolones I.TheAandBSeries 2. The C and D Series VI. The Rotenoids I. Stereochemistry. 2.Deguelin 3. Elliptone 4. Munduserone 5. (X. Toxicarol. 6. Sumatrol. 7. Malaccol 0 8. Pachyrrhizone 9. Erosone10. Dolineone VII. Biogenesis anq Biogenetic Connections of the Rotenoids VIII. Synthesis in the Rotenoid Group Addendum. References.

326

~40

Namenverzeichnis. Index of Names. Index des Auteurs

Sachverzeichnis. Index of Subjects. Index des Matieres

Inhaltsverzeichnis.


2

3

4

4

5

~,

17

18

19

.23

26

l'

Photochemische Umwandlungen ausgewahlter Naturstoffe. Von KURT

SCHAFFNER, Laboratorium rur organische Chemie, Eidgenossische

Technische Hochschule, Ziirich I. Einleitung II. Zum Mechanism1is photochemischer Reaktionen III. Fragmentierung von Carbonylverbindungen I. Spaltung von (X,p-standigen C-C-Bindungen. 2. Spaltung zu Acyl-Alkyl-Radikalpaaren Rekombination des Radikalpaares 6. -Intramolekulare Dis-

proportionierung des Radikalpaares 8. -Decarbonylierungen 13.

3. Acylwanderungen IV. Geriistumlagerungen alicyclischer Ketone. I. (X.p-Epoxy-ketone 2. Konjugierte Cyclohexenone 3. Gekreuzt konjugierte Cyclohexadienone Prima.re Umwandlungen der gekreuzt konjugierten Dienone 27. -

Umwandlungen der ketonischen Photoisomeren 31. -Modifikationen

des Isomerisierungsverlaufs gekreuzt konjugierter Dienone 35. -

Umwandlungen in phenolische Photoisomeren 36.

V. Ringkontraktionen cyclischer Diazoketone 38

VI. Intramolekulare Substitutionen unter Wasserstoffverschiebung 4°

I. Diazoketone 46

2. Hofmann-Loffler-Freytag-Reaktion. 47

3. Nicht-konjugierte Ketone und Aldehyde. 48

4. Nitritester. 52

5. Hypojodite 56

6. Hypochlorite. 57

7. Alkyl- und Saureazide 58

VII. Umwandlungen von Doppelbindungssystemen 61

I. Cis-trans-Isomerisierung. 61

2. Suprasterin2-II und ,13;6-Cholestadien 63

3. Homoannulare Diene 65

Ringspaltung zu Trienen 65. -Cyclisation zu Cyclobuten-

Derivaten 69.

4. Cycloheptadienone. : ...

5. Tropolone6 G ..

tu 1 d A 5.7.9.1l St .d.erus m a~erun~ er erO1 e.

71

7277

78

81

88

9.;

7. Doppelbindungswanderungen 8. Cycloadditionen VIII. pyrimidine, Riboflavin und Aminosauren .

Literaturverzeichnis

Stilbene im Pflanzenreich. Von GERHARD BILLER, Organisch-chemischesInstitut der Universitat Wien , 115

I. Historischer Oberblick 116

II. Isolierungund Konstitution 117

I. Struktur.: 117

2. Physikalische Eigenschaften 120

3. Isolierungsmethoden 120

4. Nachweismethoden 121

5. Konstitutionsaufklarung 122

6. Konfiguration 123

III. Synthesen 124

I. Stilbene 124

2. Stilbencarbonsauren und 3.4-Dihydro-isocumarine 125

IV. Vorkommen und Eigenschaften 127

I. Stilbene und Stilbenglucoside 1274-Hydroxystilben 127. -4-Methoxystilben 127. -Pinosylvin 127. -Pinosylvin-monomethylather 127. -Pinosylvin-dimethylather 127. -

Resveratrol 128. -Piceid 128. -Pterostilben 128. -Oxyresvera-trol 128. -Chlorophorin 128. -Piceatannol 129. -Rhapontigenin 129.-Rhaponticin 130. -3,5,3'.4',5'-Pentahydroxystilben 130. -

3,5.3' ,4'.5'-Pentahydroxystilben-glucoSid 13 I.

2. HydrangenolundPhyllodulcin 131

Hydrangenol 131. -Hydrangenol-8-p-D-glucosid 131. -Hydrangea-saure 132. -D-Phyllodulcin 132. -DL-Phyllodulcin 132.

V. Verteilung im Pflanzenreich 133

I. Systematische Obersicht 133

2. Verteilung u.nd Bildung im pflanzlichen Gewebe 133

3. TaxonomischeBedeutung 136a) In der Gattung Pinus 136. -b) In der Gattung Eucalyptus 137.

VI. Biologische Wirkung. 137

I. Kemholz-Inhaltsstoffe 137

2. Stilbene aus anderen Pflanzenorganen VII. Biosynthese. I. Hypothesen : .,,~

2. Experimentelle Befunde 141a) Pinosylvine 141. -b) Piceid und Rhaponticin 142. -c) Oxy-resveratrol 142. -d) Hydrangenol 142.

3. Zusammenfassung 144

T;i-..r"i-i,ru..r7..;..hn;"

139

139.1~

T"h

"'

l

vInhaltsverzeichnis. -Contents. -Table des niatieres.

,

"

A Pattern of Development in the Chemistry of Pentacyclic Triterpenes.

By T- G- HALSALL and R- T- APLIN, The Dyson Perrins Laboratory,

University of Oxford 153

I. The Classical Era of Triterpene Chemistry 153

II. General Developments since 1949 155

I. Relationships between the Different Pentacyclic Skeletons 1552. StereocheInistry 156

3. Biogenesis. 1564. New Techniques of Analysis 159

lll- \,,)1n~~t 11~~1l~ \~ t\).~ \,,\).~'ffi\~t1)1 t>i '?~~'t'a.t"yt\\t ~n't~TI>~~~~ "l{){)

I- Platanic Acid 1612- Triterpenes from Ferns 1613. C(18)-Nor-triterpenes- 162

4- A-Seco-triterpenes 1635. Ceanothic Acid and Related Compounds. 1656. More Highly Oxygenated Pentacyclic Triterpenes. 166

rv. Tabulation of Data 16g

Table I- Pentacyclic Triterpenes of Known Structure 17°

Table 2- Classified List of Pentacyclic Triterpenes 18cArborane System 180- -Hopane System 180. -Lupane System 182. -

Oleanane System 183- -Ursane System 186-

.Table 3. Pentacyclic Triterpenoids of Unknown Structure. 18~

References 19c

Griseofulvin and Some Analogues. By JOHN FREDERICK GROVE,

London School of Hygiene and Tropical Medicine (University of London) 203

I- Introduction. 204

II. The CheInistry of the Grisans 20~

I. Nomenclature 205

2- Isolation of Fungal Grisans 201a. Griseofulvin 201b. Griseofulvin Analogues 20~

3- Structure and Absolute Configuration of Griseofulvin 20~a. Structure 20~

Oxygen FuD£tion 208- -Oxydative Degradation 209- -Fission

Giving Rings A and C 212-b- Absolute Configuration 21~c- Structures of Griseofulvin Analogues. 21(

4. General Reactions 211a- Functional Derivatives of Carbonyl Groups 211

3-One 217- -2'- and 4'-Ones 217.b- Reduction of the Carbonyl Groups and Their Regeneration. 21~

3-One 218. -2'- and 4i-Ones 219.c- Hydrolysis and Alcoholysis of Ether Linkages: O-Alkylation. 21!

2'- and 4'-Ethers 219. -6-Ethers 221. -4-Ethers 223.

d. Nucleophilic Substitution 22:Ether Exchange 223. -Amino Compounds 223- -Enol Chlo-

rides 22~. -Ring A 22i.

e. Halogenation and Dehalogenation 2262',~'-Diones 226. -2',4'-Dione Enol Ethers 226.

f. Nitration. 227g. C-Alkylation : 228h. Olefin-forming Eliminations and Dehydrogenation. 229i. Catalytic Reduction 229

(d,d)-2'-Ene 229. -(l.d)-2'-Ene 231. -3'-En.e 232. -2'- and

4'-Ones 232. -5'-Ene 233.j. Molecular Rearrangement Leading to Substituted Dibenzofurans .233

Formation 233. -Synthesis 234. -Related Systems 235.k. Other RingC Fissions 235I. Fission of Ring B 236

2',5'-Dien.-3,4'-diones 236. -2'-En-3,4'-diones 238.

5. Optical Properties. 238a. Ultraviolet Spectra. 238b. Infrared Spectra 240c. Nuclear Magnetic Resonance Spectra. 241d. Optical Rotatory Dispersion 241e. X-ray Data :. 242

6. Detection and Estimation 242

m. Synthesis 242

a. Condensation of Coumaranones with Dihalogenoalkanes 243b. Double Michael Addition of Ethynyl Vinyl Ketones to Coumaranones 244c. Cyclisation of 2.2-Disubstituted Coumaranones (Ester Synthesis) ...244d. Usnolic Acid Route. 248e. Intramolecular Phenol Radical Coupling. 250f. Cyclisation of I-~ryloxycycloalkane Carboxylic Acids. 252

JV. Biosynthesis 253

V. Metabolism. 258

References. 2'i8

265

265

266266

270271

272272273

273273

274274

27527.S

The Chemistry of Toxins Isolated from Some Marine Organisms.

By PAUL J. SCHEUER, Department of Chemistry, University of

Hawaii, Honolulu. 1.lntroduction II. Toxins Isolated from Chordates I. Tetrodotoxin 2. Pahutoxin 3. Ciguatoxin IU. Toxins Isolated from Echinoderms I. The Holothurins 2. Star Fish Sa~onins [V. Toxins Isolated from Mollrisks Saxitoxin. : ..' V. Toxins Isolated from Annelids Nereistoxin VI. Toxins Isolated from Coelenterates Palvtoxin ,

~

VII. Toxins Isolated from Protozoans. .

Saxitoxin. VIII. Conclusion References.275

275

;. .; 275

276

Siderochrome. (Natiirliche Eisen(III) -trihydroxam~t- Komplexe.)

Von W. KELLER-SCHIERLEIN. V. PRELOG und U. ZAHNER. Labora-

torium fiir organische Chemie, Eidgenossische Technische HoChschule,

Zurich. 279

I. Einleitung 280

II. Bi010gie der Sideramine und Sideromycine. 281

I. Der Nachweis Von Sideraminen 281

2. Der Nachweis Von Sideromycinen 2833. Das Vorkommen der Sideramine 2834. Das Vorkommen der Sideromycine 2855. Die antibiotische Wirkung der Sideromycine. 2866. Beziehungen zwischen Sideraminen und Sideromycinen 286

7. Die Wirkungsweise der Sideramine 287

III. Is01ierung und Charakterisierung der SideroChrome 289

I. Craig-Verteilung 2902. Ionenaustauscher-Chromatographie 2903. GegenstromelektrophoreSe .2914. Verteilungschromatographie 2915. Charakterisierung der SideroChrome. 291

IV. Sideramine aus Actinomyceten (FerrioXamine) 292

I. Konstitution. 2922. Synthese 297

V. Sideramine und bi010gisch nicht wirksame SideroChrome aus Pilzen ..298

Die CarbonSaUre-Bausteine 299. -Die AminoSaure-Bausteine 300. -

Der Aufbau der Sideraminmo1eklile aus den Bausteinen 302.

VI. Sideromycine , 306

I. Konstitution des FerrimycinsA1 3062. Konstitution des d2-Albomycins 308

VII. Andere HydroxamSaUren aus Mikro0rganismen 311

VIII. Desferri-sideroChrome als Komplexbildner 313

I. Komplexstabilitaten 3132. Die Anwendung Von Desferrioxamin Bin der Humanmedizin 316


Namenverzeichnis. Index of Names. Index des Auteurs. 323

Sachverzeichnis. Index of Subjects. Index des Matieres . 339

.

Inhaltsverzeichnis.


Polysaccharides of Marine Algae. By STANLEY PEAT and J. R.

TURVEY, Department of Cl;1emistry. University College of North

Wales.Bangor.Caernarvonshire..." I

I. Introduction. 2

II. Skeletal Polysaccharides of the Algal Cell-Wall 4

I. Cellulose in Algae. 5

2. Mannans. 7

3.Xylans 8

4. Conclusions. 10

III. Food Reserve Polysaccharides ; II

I. Starch (Green Algae) II

2. Floridean Starch (Red Algae) 13

3. Laminarin (Brown Algae) 14

4. Conclusions. 16

IV. Polysaccharides Containing Sulphate Esters 17

I. Fucoidin {Brown Algae) 17

2. Galactan Sulphates of Red Algae 19

(a) Agarose Type 19

{i) Agar 19. -{ii) Funori 22. -{iii) Porphyran 23.

{b) ,,-Carrageenan Type 24

{i) Carrageenan 24. -{ii) Furcellaran 27. -{iii) Other Carra-

geenan Types 28.

{c) Miscellaneous. 28

{i) The Mucilage of Dilsea edulis 28. -{ii) Polysiphonia fastigiata 29.

-3. Polysaccharide Sulphates of Green Algae. {a) Heteropolysaccharides Containing Sulphated Arabogalactans ;)V

{i) Cladophora rupestris 30. -{ii) Caulerpa filiformis 31. -

{iii) Codium fragile 32.

{b) Heteropolysaccharides Containing Glucuronic Acid. , .32

{i) Ulva lactuca 32. -{ii) Acrosiphonia centralis 34. -{iii) Entero-

.morPha compressa 35.

4. Conclusions V. Alginic Acid References.

3°

: 35

36

~o

-

:rv..Inhaltsverzcichnis. Contents. Table des matiere!

46465154

55

57

57

Der Kohlenhydratstoffwechsel in Gerste, Hafer und Rispenhirse. Von

H. H. SCHLUBACH, Physiologisch.Chemisches Institut der Universitat

Miinchen. I. Die los1ichen Kohlenhydrate in der Gerste und ihre Konstitution , II. Die loslichen Kohlenhydrate im Hafer und ihre Konstitution III. Die loslichen Kohlenhydrate in der Rispenhirse und ihre Konstitution. .

IV. Die enzymatische Steuerung d~s Kohlenhydratstoffwechsels in den

Getreidearten V. Zur Geschichte der Kultur der Getreidearten Literaturverzeichnis

The Chemistry of Biological Sulfonium Compounds. By FRITZ SCHLENK,

Argonne National Laboratory, Argonne, Illinois. 61

I. Introduction. 62

II. The Discovery of Sulfonium Compounds. 62

III. The Chemistry of Sulfonium Compounds. 64

I. Formation and Structure 64

2. Mechanisms 6f Decomposition and Rearrangement. 65

3. Stereoisomerism of the Sulfonium Group. 68

IV. In vitro Synthesis and Properties of Biological Sulfonium Compounds.. 69

I. Dimethyl-p-propiothetin 6g

2. S-Methylsulfonium Salt of Methionine (S-Methylmethionine) 7°

3. S-Adenosylmethionine and Related Compounds. 72a. In vitro Synthesis of S-Adenosylmethionine 72b. S-Adenosyl-3-methylmercaptopropylamine 74c. Hydrolysis of S-Adenosylmethionine 74d. Effect of Alkali on S-Adenosylmethionine and Related Compounds 76e. Diastereoisomers of S-Adenosylmethionine. 81

V. Origin and Metabolism of Biological Sulfonium Compounds. 83

I. Dimethyl-p-propiothetin 83

2. S-Methylsulfonium Salt of Methionine (S-Methylmethionine) 85

3. S-Adenosylmethionine ;... 86

VI. Metabolic Functlons of ~iological Sulfonium Compounds. 88

I. Transmethylations : 88a. General Considerations 88

b. The Diversityof Methyl Acceptors 91c. Analytical Techniques 93d. Attempts to Explain the Mechanism of Transmethylation. 94

2. B~osynthesis of Spermidine and Spermine. ...;. 96

3. Formation of Homoserine.Lactone and Homoserine from S-Aden.osyl-methionine 96

VII. Derivatives and Analogues of Biological Sulfonium Compounds. 98

I. Analogues for Metabolic Studies 982. Sulfonium Derivatives of Protein-bound Methionine IOJ.

RAfArAncA" 104.

..

"

.

Some Aspects of tQe Chemistry and Function of Human and Animal

Hemoglobins. By WALTER A. SCHROEDER, California Institute of

Technology, Pasadena, California, and RICHARD T. JO~,ES, Divisionof Experimental Medicine, University of Oregon Medical School, Port-

land, Oregon. 113

I. Introduction. 115

II. Nomenclature ' 116

III. The Amino Acid Sequence of Human Hemoglobins A and F 116

I. HemoglobinA 117a. The Amino Acid Sequence of the IXA Chain. 118b. The Amino Acid Sequence of the pA Chain. 118

2. Hemoglobin F 119a. The Amino Acid Sequence of the IXF Chain. 119b. The Amino Acid Sequence of the "F Chain. 120

3. A Comparison of HemoglobinsA and F 120

4. A Comparison ofthe IX and pChains 121

IV. Other Hemoglobins in the Normal Human Individual 121

I. The Hemoglobin Components of the New-born Infant. 122

2. The Hemoglobin Components of the Adult. , 123

V. The Abnormal Human Hemoglobins 126

I. Methods. 127

2. Nomenclature. 132

3. Some General Genetic Considerations 133

4. Hemoglobins with Abnormalities in the IX Chain. 134

5. Hemoglobins with Abnormalities in the p Chain. 134

6. Hemoglobins with Abnormalities in the" Chain. 134

7. Hemoglobins with Abnormalities in the d Chain. 135

8. Hemoglobins with Other Abnormalities. 135

9. General Remarks 136

VI. Animal Hemoglobins 136

I. Gross Structu.re of Animal Hemoglobins. 137

2. Adult and Fetal Forms 138

3. Nomenclature of the Animal Hemoglobins. 138

4. Sequences in the Animal Hemoglobins. 139a. IX Chains. 140b. p Chains. I42c. " Chains. 143

VII. Hemoglobin in Three Dimensions :..145


.2. The Relationship between Hemoglobin and Myoglobin. I45

3. Pertinent Aspects of the Structure of Myoglobin. I46

4. The IX and .B Chains -Secondary and Tertiary Structure. 147

5. The Quaternary Structure 155

VI

6. The Three-dimensional Structure of Hemoglobins from Different

Species 1567. Oxygenation and Structural Alterations. 156

VIII. Chemical Modifications of Hemoglobin. 157

I. Introduction 157

2. Reactions of the Heme Group 158

3. Titration Curves and their Interpretation. 158

4. Reactions of the Sulfhydryl Group 159

5. Other Reactions 160

6. Conclusions 160

IX. Reversible Dissociation and Subunit Hybridization of Hemoglobin. ..160


2. Possible Modes of 1;)issociation 161

3. Evidence for Dissociation 162

4. Mechanism of Dissociation and Subunit Hybridization. 162

5. Other Factors which Influence Dissociation and Subunit Hybridization 165

6. Comments on Dissociation and Hybridization. 166

X. The Biosynthesis of Hemoglobin 169


2. Genetic Control of Hemoglobin Structure. 17°

3. Biosynthesis of the Polypeptide Chains of Globin 172a. The Activation of AInino Acids for Protein Biosynthesis. 173b. DNA and the Role of m-RNA 174c. The Function of the Ribosomes 175d. The Assembling of the Polypeptide Chain. 176e. The Final Release of the Protein 177

4. BioSynthesis of Heme 179

5. The Attachment of Heme to Globin Chains. 179

6. Assembly of Chains into the Whole Hemoglobin Molecule. 180

References 181

195

Tnfi

IQ8

20720720&

208

208211

Kollagen. Von W. GRASSMANN, unter Mitarbeit von J. ENGEL, K.

HANNIG, H. HORMANN, K. KfjHN und A. NORDWIG, Max-Planck.

Institut fiir EiweiB- und Lederforschung. Miinchen. I. Ein1eitung. II. tJbersicht III. Aminosaurezusammensetzung I. Kollagene der Wirbeltiere 2. Kollagene im niederen Tierreich IV. Primarstruktur : I. Aminosauresequenzen des Kollagens ~ Dn~~tt~ <;:"..~~- ..n-1 AI1r"l;-HvnTnlv..,,

VIIInhaltsverzeichnis. -Contents. -Table des matieres.

b. Enzymatische Methoden 2II(X) Abbau des denaturierten K011agens mit Trypsin 2 I I. -P) K01-lagenase -der Schliissel fiir die ap01aren Bereicl1e 220. -

y) Is01ierung der ap01aren Bereiche 223. -b) Is01ietung derp01aren Bereiche 227.

2. Alkali- und Hydroxylamin-empfindliche Bindungen, Endgruppenund Acetylgruppen 232

3. Quervernetzungen 235

V. Sekund'J.r- und Tertiarstruktur 238

I. Ergebnisse der Rontgenstruktur-Untersuchung 238

2. Physikaliscl1e Eigenschaften des nativen K011agenm01ekills 245

3. Denaturiertes IOsliches K011agen 248

VI. Zerfall und Riickbildung der Sekundar- und Tertiarstruktur (De- und

Renaturierung) 25II. Denaturierung in LOsung 25I

2. Denaturierung im festen Zustan,d (Schrumpfung) 254

3. Renaturierung in LOsung 255

4. Der De- und Renaturierung des K011agens analoge Umwandlungen Von

(Pro.Gly.Pro)ninLOsung 263

VII. Bau und Bildung der Fibrillen und Segmente (Quartarstrukturen) ...264

I. Die nativen Fibrillen , 264a. Das Querstreifungsmuster 264b. Die Ursache der Querstreifung 264

2. Der m01ekulare Bau der verschiedenen K011agenstrukturen 266a. Das Querstreifungsmuster der Long-spacing-Segmente (SLS) 266b. Die Anordnung der K011agenm01ekille in den Fibrillen des nativen

Typs 268c. Die Anordnung der Molekille in den Long-spacing-Fibrillen (FLS) 269d. Die End-an-End-Zusammenlagerung der K011agenm01ekill~ , 27°

3. Die FibriUenbildung 273

4. Die Beeinflussung der Fibrillenbildung in vitro 274

VIII. Stoffwechsel des K011agens 276

I. Biosynthese , 276

2. Reifung und Alterf1ng 284

3. Abbau im Korper 287

4. Mineralisierung. 289

5. K011agenosen. 290

Literaturverzeichnis. 293

,

~

Some Applications of Nuclear Magnetic Resonance Spectroscopy in .

.Natural Product Chemistry. By L. M. J ACKMAN , Department ofChemistry, University of Melbourne, Australia. 315

I. Introduction 315

II. Principles of Application , 318

Vffi

318

319

321

321

330

333

337

337

341

344

349

356

~60

I. Determination of Empirical Formulae. 2. Determination of the Classes of Protons in a Molecule. The Chemical

Shift. 3. The Number of Protons in a Given Class. Intensities. 4. The Sequence of Groups in Molecules. Electron Coupled Spin-Spin

Interaction ; 5. An Example of Application to Structure Determination. 6. Applications to the Elucidation of Relative Stereochemistry and Con-

formation III. Examples in Natural Product Chemistry I. Steroids 2. Carbohydrates. 3. Carotenoids and Acyclic Terpenes 4. Flavonoids and Related Compounds 5. Alkaloids References.

363Namenverzeichnis. Index of Names. Index des Auteurs

~~,.hvAr..A;'.hn;~ TntiAv nf S,1hi.."t_~- Inrl"x rl"s Matier"s

.

Inhaltsverzeichnis.


,

J

t

Mass Spectrometry of Selected Natural Products. By KLAus BIEMANN,

Department of Chemistry, Massachusetts Institute of Technology,Cambridge, Massachusetts I

I- Introduction. 2Instrumentation. 6Principles of the Interpretation of Mass Spectra. 8

II- Indole Alkaloids 13I- Correlation of Closely Related Alkaloids- 13

Correlation of the Carbon Skeleton 13-2- Dihydroindole Derivatives 16

Aspidospermine Skeleton 19. -Vincadifformine 24. -Akuammicineand Condyloc&rpine 26. -Ajmaline 34-

3- Indole Derivatives. 37Sarpagine 37. -Eburnamine 40- -Yohimbines 40. -Oxindolesand PseudOindoxyls 42-

4. 'Dimeric' Indole Alkaloids 46Voacamine 46. -Vinblastine 48- -Pleiomutine 49. -Villal-

stonine 51.

111- TetrahydroisoquinolineAlkaloids 54Aporphine Alkaloids 55- -Xylopine 56. -Protopine 57- -PapaverAlkaloids 58.

IV- Bisbenzyl-tetrahydroisoquinoline Alkaloids. 59

V. Polycyclic Tetrahydroisoquinoline Alkaloids. 62Amaryllidaceae Alkaloids 62- -Morphine 64-

VI. Miscellaneous Alkaloids and Other Nitrogen Containing Natural Pro-

ducts. 65

VII.. Quarternary Bases 67

VIII. Natural Products Other than Alkaloids 69Lipids 69- -Steroids 7°. -Carbohydrate Derivatives 71- -

Nucleosides 72. -Amino Acid Sequence in Oligopeptides 73-

IX- High R~solution Mass Spectrometry 77Element Map 82. -Computer Interpretation 85-

References: 86

Pflanzliche Steroide mit 21 Kohlenstoffatomen. Von RUDOLF

TSCHESCHE, Organisch-chemisches Institut der Universitat Bonn. 99

I. Einleitung 100

II. N-freie Pregnanderivate aus Scrophulariaceen 102Die Struktur der einzelnen Aglykone 102

a. Diginigenin 102. -b. Digifo1ogenin 103. -c. Digipurpurogenin 103. -d. Digiprogenin 104. -e. Purpnigenin 105. -f. Purprogenin 1°5. -

g. Digacetigenin 105.

IV

~III. N-freie Pregnanderivate der Asclepiadaceen. 106Die Struktur der einzelnen Aglykone 108

a. Pregnen010n und Allopregnan010n 108. -b. Weitere Aglykone ohneOH an C(8) : Benzoylramanon. Pergularin, Utendin, Tomentogenin 108.-c. Aglykone mit OH an C(8) : Cynanchogenin. Line010n. Sarcostin.Penupogenin, Tayl0ron. Metaplexigenin 109. -d. Aglykone mit einerGlyk01gruppierung an C(1l) und C(12) : Drevogenine A, B, D und P,Kondurangogenin A 110.

IV. N-freie Pregnanderivate aus Apocynaceen IIIa. Progesteron 111. -b. H01adyson 111. -C. Ketone aus Pa1'avalla1'ismic1'ophylla 112.

V. N-haltige Pregnanderivate aus Apocynaceen 113a. An C(3) aminierte Derivate. OH an C(IO) : Funtumidin, H01adysamin,H01aphyllidin 14. --b. An C(3) aminierte Derivate, Ketogruppe C(20P5 <X : Funtumin, H01amin, H01aphyllamin, H01aphyllin 115. -c. AnC(3) aminierte Derivate mit weiteren O-Funktionen im M01ekiil bzw.keine an C(20). L16: H01adysin, Kurchilin, Kurchiphyllin, Kurchiphyll-amin 116. -d. Paravallarin-Typ (Lactonring E), L16: Paravallarin,Paravallaridin, Kibatalin 116. -e. Nur an C(20) aIninierte Derivate,5 <X : Funtuphyllamine A, B, C, Funtumafrine B und C, H01afebrin.Conopharyngin, Irehamin, Irehin (= Buxomfgin). Terminalin 117. -f. An C(3) und C(20) aminierte Derivate: Chonemorphin, Malouetin,EpipachysaInine A (= Saracodin), B, C (Dictyodiamin), D, E undF, Pachysamine A und B, N -Methylpachysamin A 119. -g. An C(3) undC(20) aminierte Derivate, 5<X und weitere O-Funktionen im M01ekiil:Malouphyllin, Pachysandrine A, B. C und D. Basen XI und XIIIaus P. te1'minalis, O-Desacyl-pachysandrin B 120. -h. An C(3) undC(20) aminierte Derivate und L16: Irehdiamine A und B, Kurchessin(= Saracodinin?), Saracoccin (= Saracocin). 3<X.20S-Bisdimethyl-amino-L16_pre~en 122. -i. An C(3) und C(20) aIninierte Derivate miteiner OH-Gruppe an C(18P L16: Holarrhimin, Monomethylh01arrhimine Iund II, Tetramethylh01arrhimin, H01arrhidin 122. -j. Conessin-derivate mit O-Funktionen an C(3) bzw. C(7P L16: Latif01in. Norlatif01in,Latif01inin. Funtulin, Funtudienin. H010namin 124. -k. Conanin-derivate mit N-Funktion an C(3P 5 <X : Malouphyllamin. Dihydro-conessin,Dihydro-conessimin, Dibydro-conkuressin, Funtessin 126. -1. Conenin-derivate mit N -Funktion an C(3P L16 : Conarrhimin, Conamin, Conessimin,Conimin, Isocpnessimin. Conessin, 7<X-Hydroxyconessin, 12 p-Hydroxy-conessin, H01afrin, H01arrhenin. H01arrhetin 127. -m. Conanin-derivatemit DoppelbindungenL16.18: Conkurchin (= Irehlin), Conessidin 132. -n. Kurch01essin 133. -0. D-Homo-androstan-AlkaI0ide: Dicty01ucidin.Dicty01ucidamin 134.

VI. Pregnen010n als biogenetische Vorstufe fiir Digitan01e, Cardenolide.Bufadien01ide und Aminopregnan-derivate 135


Cyclite: Biosynthese, Stoffwechsel und Vorkommen. Von H. KINDL

und 0. HoFFMANN-osTENHoF, Organisch-chemisches Institut derUniversitatWien : 149

I. Einleitung 150II. Nomenklatur der Cvclite 154

vInhaltsverzeichnis. -Contents. -Table des matieres.

1-

1;

r

A. Schreibweise der-Formeln 155B. Bezifferung der Ringkohlenstoffatome : 155C. Benennung der Verbindungen 155D- Bezifferung der optisch aktiven Cyclite; Richtungssinn def Bezifferung 156

III. Biosynthese 156A. Biosynthese des myo-Inosits 157

I. Vorversuche ; ; 1572. Versuche mit selektiv markierten Vorstufen 159

a. Friihe Untersuchungen iiber die Entstehung von myo-Inosit inMikroorganismen 159. -b. Untersuchungen iiber die Entstehungvon myo-Inosit aus D-GlucoSe in hoheren Pflanzen 161. -c. Unter-suchungen iiber die Biosynthese von myo-Inosit aus D-Glucose inTieren 162.. -d. Neuere Untersuchungen iiber die Umwandlungvon D-Glucose in myo-Inosit in Mikroorganismen 163. -e. Unter-suchungen iiber den Mechanismus der Umwandlung von D-Glucosein myo-Inosit und iiber Zwischenprodukte dieser RingschluBreak-tion 164.

B. Biosynthese der Methyla.ther des myo-Inosits 166C. Biosynthese von Glykosiden des myo-Inosits 167D. Die Herkunft des myo-Inosit-Restes in Phytinsa.ure und in den PhoS-

phoinositiden 167E. Bildung von scyllo-Inosit 16gF. Bildung Von D-chiro-Inosit und D-Pinit 170G. Bildunr; Von L-chiro-Inosit und seiner Methyla.ther 171H. Bildung von L-Quercit, L-Viburnit und L-Leucanthemit i72I. BildungvonAmino-desoxycycliten 173

IV. Katabolischer Stoffwechsel 174A. Oxydationsreaktionen unter Erhaltung der Cyclitstruktur 174B. Oxydative Aufspaltung des Cyclohexanringes 176

I. Abbau im tierischen Organismus oder durch Enzympra.paratetierischer Herkunft 176

2. Oxydative Aufspaltung durch Mikroorganismen und durch Enzymemikrobiellen Ursprungs 177

3. Oxydative Aufspaltung in hoheren Pflanzen 178

V. Vorkommen der Cyclite 179A. myo-Inosit 180. -B. Methyla.ther des myo-Inosits 180. -C. scyllo-Inosit 181. -D. D-chiro-Inosit und seine Methyla.ther 181. -E. L-chiro-Inosit und seine Methyla.ther 181. -F. DL-chiro-Inosit 181,. -G. Methyl-a.ther des muco-Inosits 181. -H. Derivate des neo-Inosits 181. -

I. C-Methylinosite 181. -1. Cyclohexanpent01e und Cyclohexentetr01e 182.-K. Amino-desoxycyclite 182.

VI. Tabellen 184


The Chemistry of the Order Cupressales. By H. ERDTMAN, Department

of Organic Chemistry, Royal Institute of Technology and T. NORIN,

Swedish Forest Products Research Laboratory, Stockholm. 206.


II. Botanical Classification of the Order Cupressales 208~

..

III. Chemical Constituents of Cupressales 209

I. Cyclitols and Simple Phenols 209

2. Lignans 212

3. Flavonoids and Biflavonyls 213

4. Leaf Waxes and Other Less Investigated Constituents. 214

5. Tropolones 216

6. Terpenes. 220a. Monoterpenes ., 221

Thujic Acid 221. -Chamic and ChaIninic Acids 222. -ShonanicAcid 223. -Other Monoterpene Acids from Calocedrus to1'mosana 225.

b; Sesquiterpenes 225Nerolidol '225. -Bisabolanes 225. -Humulene and Caryophyl-lene 225. -Eleli1anes 226. -Selinanes 226. -Eremophilanes 228.-Cadinanes and Related Terpenes 229. -Longifolene and Juni-perol 229. ~ Cedranes 231. -ThujopsaneS 232. -Widdrol 233. -

Cuparanes 234.c. Diterpenes. 235

Labdanes 236. -Pimaranes 237. -Rimuene 238. -Ferruginoland Related Terpenes 238. -Totarol and Related Terpenes 240.-Phyllocladene and Related Tetracyclic Diterpenes 241. -

Verticill01 242.d. Triterpenes 243e. Biogenetic Aspects. 243

IV. Some Chemotaxonomic Aspects 247Phenolic CompoUnds 247. -Trop010nes 248. -Terpenes 25°. -General

Remarks 252.

V. Chemical Constituents of Cupressales Species. 253

VI. Tables 257

I. Distribution of Lignans in Cupressales 257

2. Physical Constants of Lignans from Cupressales 258

3. Distribution of Biflavonyls and Composition of Leaf Waxes in Cupres-

sales 259

4. Physical Constants of Biflavonyls from Cupressales 260

5. Distributio, of Tropolones in Cupressales 261

6. Physical Constants of TrOpolones from Cupressales 263

7. Distribution of Selinanes, Guaianes and Related Sesquiterpenes in

Cupressales 2648. Distribution of Cadinanes and Related Sesquiterpenes in Cupressales 265

9. Distribution of Sesquiterpenes in Cupressales: Caryophyllane, Humu-lane, Longifolane, Cedrane, Thujopsane and Cuparane Types. 266

10. Physical Constants of Ses.quiterpene Hydrocarbons from Cupres&:ales 268

II. Physical Constants of Sesquiterpene Alcohols from Cupressales. 26912. Physical Constants of Sesquiterpene Aldehydes, Ketones and Acids

from Cupressales : 274

13. Physical Constants and Distribution of Diterpenes in Cupressales 270

~A.A~A.."AQ 27 -~

Quinone Methides in Nature. By A. B. TURNER, Department of Chemistry,

University of Aberdeen, Old Aberdeen, Scotland. ...': 288

I. Introduction. ; .,; 288

II. Stable Quinone Methides in Nature 289I. Citrinin. 2892. Pulvilloric Acid. 2923. Ascochitine. 2964. Purpurogenone 2985. Fuscin. 2996. Celastrol and Pristimerin., 3017. The Perinaphthenone Group 305

a. Haemocorin 305b. Atrovenetin and Herqueinone 307c. Biogenesis of Plant and Fungal Perinaphthenones. 310

8. Anhydro Bases of the Flavonoid Series. 312

9. General Discussion 314a. Structural Features <;:.ontributing to Stability. 314b. Tautomeric Forms 314c. General Reactions 316

III. Quinone Methides as Intermediates in Biochemical Processes. 316

I. Oxidative Phosphorylation 3162. Oxidative Metabolism 3203. Miscellaneous Processes 321

References. 321

.1

1

1~

1

'1

The Pyrrolizidine Alkaloids. II. By F: L. WARREN, Natural Products

Research Unit, University of Cape Town, Rondebosch, Cape, South Africa 329

I. Introduction: Occurrence and Nature of the Pyrrolizidine Alkaloids. ..330

II. The Free Bases and the Basic Hydrolysis Products. 331

I. The Absolute Configurations 331

I-Hydroxymethylpyrrolizidines 333. -7-Hydroxy-I-hydroxymethyl-pyrrolizidines 335.

2. New Bases. 335Otonecine 337. -Loline, Lolinine, Norloline and Fusticine 338.

.3. Syntheses of the "Necine" Bases 340

pyrrolizidine 340. -I-Methylpyrrolizidine 341. -I-Methylene-pyrrolizidine 341. -3-Methyl- and 3-Hydroxymethylpyrrolizidines 342.

-I-Hydroxymethylpyrrolizidines 342. -Dihydroxymethyl-

pyrrolizidines 344.

III. The Acids Associated with the Pyrrolizidine Alkaloids. 346

I. Clo-Adipic Acids and Retusanecic Acid. 346

Hygrophyllinecic Aci~ 346. -Seneciphyllic, Isoseneciphyllic,"Spartioidinecic" and Riddellic Acids 348. -The Acids from, and theStructures of Jacobine, Jacoline and Jaconine 349. -Synthesis ofIntegerrinecic and Senecic Acids 353. -The Synthesis of DihydrosenecicAcid 355. --, Sceleranecic and Sceleratinic Acids 355. -Sarracinic and

Mikanecic Acids 358.

VIII Inhaltsverzeichnis. -Contents. -Table des matieres.

2. The Glutaric Acids. 358Monocrotalic, Dicrotalic, Fulvinic and Crispatic Acids, and the Acidsfrom Retusine 358. -Trichodesmic and Junceic Acids 359. -

Grantianic Acid and "Retusaminecic" Acid 360. -C-:.'Acids: Hydr-oxylated 2-Methylpentane-3-carboxylic Acids 360. -Latifolic Acid 362.-Heliotramide 363.

IV. The Structure of the Native Alkaloids : 364I. The Alkaloids Containing the C1o-Adipic Acids. 365

Seneciphylline 365. -Spartioidine 365. -Ultraviolet and InfraredSpectra in the Study of Geometrical and Stereo-isomerism: Seneciphyl-line, Spartioidine, Senecionine, Integerrimine and Usaramoensine 365.-Retusamine, Otosenine (Tomentosine), Renardine and Onetine 367. -

General Structures 367. -Sarracine 368.2. Dicrotaline and the Alkaloids Containing Trimethyl Glutaric Acids. ..368

Spectabiline (Acetyl monocrotaline) 368.3. Alkaloids Containing Acids with the 2,3-Dimethyl-4-isopropylglutaric

Acid Skeleton. 369Trichodesmine, Junceiae, Incanine and Grantianine 369.

4. AlkaloidsContaining Hydroxylated 2-Methylpentane-3-carboxylic Acids 371Echinitine, Echuimine, Echimidine, Heliosupine, Macrotomine andCynoglossiphine 371. -Latifoline 373. -Thesine and Thesinine 374.

V. Biosynthesis. 374Alkaloid Variation in the Plant 374. -Retronecine 374. -Senecic andRetronecic Acids 375. -Combination of Acid and Base 376.

VI. Pharmacology 376The Hepatotoxic Activityof the Pyrrolizidine Alkaloids 376. -Mechanismof the Toxic Action 377. -Possible Other Uses for Fully Saturated Pyrro-

lizidines 378.

VII. Tables. 379

References. 393

Some Aspects of Virus Chemistry. By H. FRAENKEL-CONRAT, Virus

Laboratory, LTniversity of California, Berkeley, California. 407

I. Introduction 407

II. The Chemistry of Viral RNA 408Size, Composition. and Conformation 408. -Nucleotide Sequences andEnd Groups 411. -Endoattack 412. -Ex oat tack for Identification ofEnd Groups 413. -Determination of Terminal Sequences 415. -Step-wise Degradation of RNA 416.

III. The Chemistry of Viral Protein 420Molecular Size 420. -Amino Acid Sequence 421. -Peptide Sequences 423.-Chain Conformation 424. -Relation of Viral Infectivity to the Structureand Interaction of its Components 427. -Modification of Viral RNA and

its Consequences 428.

Reference3 433

Namenverzeichnis. Index of Names. Index des Auteurs. 438

Sachverzeichnis. Index of Subjects. Index des Matieres. , 458

Inhaltsverzeichnis.


}

8

16

21

364°4449

Biogenetische Beziehungen der natiirlichen Acetylenverbindungen.

Von F. ",BOHLMANN, Organisch-chemisches Institut der Technischen

Universitat Berlin. , I. Einleitung ll. zur Biogenese der natiirlichen Acetylenverbindungen III. Biogenetische Bezienungen I. C13-Polyinen-Kohlenwasserst.offe als Vorst.ufen a) Pent.ainen 8. -b) Ent.et.rainen I2.. -.:--. c)Tet.raindien I2: -d) Ent.ri-.

indien I4. -e) Triintrien I4. -f) Endiint.rien IS. -g) Endiindien IS.

2. Verbindungenmit. mehr als I4C-At.omen 3. C14- und C13- Verbindbngen. 4. C1O- Verbindungen 5. Sauerst.off-Heterocyclen. 6. Phenylpolyine 7. Verbindungen aus Mikroorganismen 8. Spezielle Verbindungen. IV. Oberblick iiber die erforderlichen Reakt.ionsschrit.te zum Aufbau der nat.iir-

lichen Acetylenverbindungen Lit.erat.urverzeichnis

~

5°

54

l'

The Chemistry of the Hop Resins. By P. R. ASHURST, The Brewing

Industry Research Foundation, Nutfield, Surrey. 63

I. Introduction 63

II. The Hop Resins. 65

III. The Chemistry of the 1X-Acids 67Humulinic Acids. 67Iso-1X-acids. 69Synthesis-of Isohumulone 72The Acid Degradation of Humulone 74TheOxidation of <x-Acids 74

Humulinones 74. ~ Autoxidation 76.

-IV

777878

IV. The Chemistry of the .8-Acids The Acid Degradation of Colupulone. " The Oxidation of .8-Acids , Lupuloxinic Acid 78. -Autoxidation 79. -Hulupones 79.

V. Tetra-(3-methylbut-2-enyl) Derivatives of Phloracylphenones. ...

VI. Naturally Occurring Hard Resin Constituents. :. R "f"r"nces

82

83

8~

The Pseudoguaianolides. By J. ROMO and A. ROMO DE VIVAR. Insti-

tuto de QuimiGa, Universidad Nacional Autonoma de Mexico, Mexico City 90

I. Introduction. 90

II. Pseudoguaianolides Isolated from the Tribe Heliantheae 91Ambrosin 91. -Damsin 93. -Parthenin 93. -Coronopilin 94. -Psilo-stachyins 96. -Ambrosiol()6. -Hysterin97. -Cumanin97. -Peruvin 99.

-Peruvinin 100.

III. Pseudoguaianolides Isolated from the Tribe Heleniae. 100

Tenulin 100.(a) Structure and Configuration 100. -(b) Further Transformations 103.

-(c) Desacetylneotenulin 104.Bigelovin 105. -Helenalin 106. -Mexicanin A 109. -Neohelenalin 110.-Linifolin A III. -Linifolin B III. -Balduilin III. -Mexicanin C112. -Mexicanin 1112. -Aromatin 114. -Aromaticin IJ4. -Mexi-canin E 114. -Mexicanin H 116. -Flexuosins 116. -Amaralin 118.-Thurberilin 118. -Pulchellins 120. -Gaillardilin 122. -Gaillardi-

pinnatin 123. -Fastigilins 123. -Geigerinin 124.

IV. Remarks on the Application of Spectral Methods. 125

V. List of Compounds 126

R"f"T"nces 127

131

131

131

137

138

143

148

The Nonadrides. By J. K. SUTHERLAND, Department of Chemistry

Imperial College of Science and Technology, London. I. Introduction .: II. Glauconic Acid. III. Glaucanic Acid. IV. Byssochlamic Acid. V. Biosynthesis. References. :

Nati.irlich vorkommende Auronglykoside. Von L. F ARRAS und L. P ALLOSJOrganisch-chemisches Laboratorium der Technischen UIriversitat, Buda.

pest. , I. Einleitunf{ 150

150

v-

Inhaltsverzeichnis. -Contents. -Table des matieres.

II. Vorkommen und Iso1ierung der Auronglykoside 151Leptosin 152. -Aureusin 153. -Cernuosid 154. -.::.- Sulfurein 154. -

Palasitrin 155. -Maritimein 155. -Bractein 156. -Aureusidin-6-rutinoSid 157. -Bracteatin-6-g1uCOSid 157.

III. Allgemein anwendbare Methoden zur Strukturaufklarung der AUron-

glykoside 159

IV. Gegenseitige Umwandlung der AUrone und ihrer Glykoside in andereFlaVOnoide , 160

V. Synthese natiirlich vorkommender AUrone und Auronglykoside. 163I. Allgemeine Bemerkungen 1632. Anwendungsbeispiele 166

Rengasin 166. ~ Sulfurein 166. -Palasitrin 167. -Cernuosid 167. -

Max:itimein und Leptosin 167. -Bractein 167.

VI. Zur Genetik und Biosynthese der Aurone und ihrer Glykoside 168


Recent Advances in the Chemistry of Hashish. By R. MECHOULAM,

SChool of Pharmacy, Laboratory of Natural Products, The Hebrew

University, Jerusalem and Y. GAONi, Institute of Organic Chemistry,

Weizmann Institute of Science, Rehovoth. 175


II. Literature on Hashish and Scope of the Present Review. 177

III. Numbering of the Cannabinoids 178

IV. An Outline of the Chemical Research until the Early Fifties. 178

V. Isolation of Naturally Occurring Cannabinoids. 179

VI. Structural Elucidation 182Cannabinol 182. -Cannabidiol 182. -Cannabidiolic Acid 184. -

Cannabiger01184. -Al_THC 185. -Cannabigerolic Acid, Cannabin01icAcidandAl-THCAcid 186. -Cannabichromene 186. -Al(.)-THC 187.-

Cannabicycl01 187.

VII. AbsoluteConfiguration 188

VIII. Syntheses : 188

IX. Chemical Transformations in the Cannabinoid Series. 197I. Cleavage Reactions 197. -2. The Al to Al(.) Double Bond Migra-tion 198. -3. Addition of Alcohols to Double Bonds and Internal EtherFormation 198. -4. Cyclizations 199. -5. Aromatic Substitution 200.-6. Aromatization 200.

X. Biogenesis 201

XI. Tables. : ..203I. Biological Activity of the Natural Cannabinoids 203. -2. Canna-binoids, Some Physical Properties and Derivatives 204.

XII. Spectral Curves. 206

References. 208

The ToxicPeptides of Amanita Phal/oides. By THEODOR WIELAND.

Institut fiir Organische Chemie der Goethe-Universitat, F:rankfurt am Main 24

I. Introduction : 24

II. Isolation of the Toxic Ingredients 216

rn. Chemical Structure of the Toxic Peptides ~. 219

A. Phalloidin Group "... '221I. Phalloidin 221. -2. Phalloin 225. -3. Phallacidin 226. -4. Phal-lisin 227. -5. Phallin B 228. -6. Phalloidin Derivatives Obtained byChemical Reactions 228.

B A .t . G.mam m roup. ; 230I. lX- and .8'"Amanitin 230. -A1lomethyl-lX-amanitin 234. -2. 'Y-Ama-nitin. t5-Amanitin 236. -3. Amanin 236. -4. Amanullin 238.

IV. Synthetic Experiments 238

A. Amino Acids 238L-allo-HydroxyproliBe 239. -L-erythro-y,t5-Dihydroxyleucine 239. -

L-y-Hydroxyleucine 240. -L-y-Hydroxyisoleucines 24I,. -D,L-'Y,t5-Dihydroxyisoleuclnes 241. -z-Thioindole Compounds 242.

B. Cyclopeptides 243

V. Toxicological Remarks. 244

References. 246

251

251

252

253

253

254

255

257

258

261

262

263

264

Die Prolamine. Von E. W ALDSCHMIDT-LEITZ und H. KLING. Institut

flir experimentelle Biologie, 7799 Heiligenberg, Baden I. Einleitung II. Vorkommen III. Loslichkeitsverhalten, Isolierung IV. Molekulargewichte 0' V. Elektrophoretische Analyse VI. Bausteinanalyse VII. Endstandige Aminosauren VIII. Veranderlichkeit des Verhaltnisses der Einzelkomponenten in Pro-

laminen , IX. Reifungsproze6, Lagerung. Keimung X. Beziehungen zu Anthocyanogenen XI. Ernahrungsphysiologische Bedeutung von Prolaminel;l Literaturverzeichnis. 0'

Conformational Analysis of Some Alkaloids. By G. A. MORRISON,Department of Organic Chemistry, The University, Leeds. 269

I. Introduction. , : 2nO

II. Summary of the Principles of Conformational Analysis. 27°

III. Yohimbine and Related Alkaloids 279

IV. The Heteroyohimbines and Related Oxindole Alkaloids. .;. 290

V. Alkaloids of the Amaryllidaceae 299

I. Tazettine 299

2. Lycoririe and Related CompoUnds :; 301

3. Alkaloids Possessing the 5, 10 b-Ethanophenanthridine Skeleton. 304

References. 307

Namenverzeichnis. Index of Names. Index des Auteurs 318

Sachverzeichnis. Index of Subjects. Index des Matieres ...331

t

Inhaltsverzeichnis

Contents

2

2

5

6

6

10

10

12

13

18

18

18

22

26

29

32

34

3536363737383939

X-Ray Diffraction Studies of Crystalline Amino Acids, Peptides and

Proteins. By R. B. CaREY and R. E. MARSH, California Institute of

Technology, Pasadena, California Introduction. I. Outline of the X-Ray Method II. Crystal Structures of the Amino Acids I. Zwitterion Structures 2. Hydrogen Bonding. 3. Conformation of Side-Chains III. Crystal Structures of Simple Peptides I. Hydrogen Bonding in Peptides 2. The Geometry of the Peptide Group 3. Conformation of the Peptide Chain IV. Crystalline ~roteins I. Introduction. 2. Myoglobin 3. Hemoglobin. .: 4. Lysozyme 5. Ribonuclease 6. ~-Chymotrypsin 7. Carboxypeptidase A 8. Some Other Proteins. a. Insulin. b. Cytochromec c. Chymotrypsinogen d. Papain. e. Carbonic Anhydrase. f. Lactic Dehydrogenase. : g. fJ-Lactoglobulin R"f"r"nr""

TV Inhaltsverzeichnis C:ont"nt,.

48

AO

50

51

59

5960

60

62

6Q

747474

79

87R"

90

90QO

Q2

95

9808

102

104

Synthese von Peptiden und Peptidwirkstoffen. Von E. SCHRODER und

K. LjjBKE, Schering A. G., Hauptlaboratorium, MiillerstraBe 170-172,

Berlin65 Abkiirzungen Vorwort I. Biologisch aktive Peptide. II. Methoden der Peptidsynthese ; A. Prinzip der Peptidsynthese I. Konventionelle Synthesen a) Fragmentkondensation 60. -b) Schrittweise Kondensation 60

2. Synthese an fester Phase (Merrifield-Methode) B. Aminosauren und Blockierung ihrer funktionellen Gruppen. C. Bildung der Peptidbindung D. Reinigungsmethoden und Analytik III. Synthese von Peptidwirkstoffen A. Peptidhormone der Hypophyse I. Adrenocorticotropes Hormon Synthese des <x1-11-ACTH von HOFMANN et al. 75. -Synthese des

<x1-19-ACTH von LI et al. 75. -Synthese des <xl-U-ACTH von

SCHWYZER et al. 76. -Synthesen des natiirlichen ACTH 78. -

Beziehungen zwischen Struktur und Aktivitat 79

2. Melanocytenstimulierende Hormone. <x-MSH 79. -fJ-MSH 81. -Beziehungen zwischen Struktur und

Aktivitat 81

3. Oxytocin und Vasopressin Oxytocin 81. -Vasopressine 85. -Beziehungen zwischen Struk-

, tur und Aktivitat 86

B. Peptidhormone des Intestinaltraktes I. Gastrin. Beziehungen zwischen Struktur und Aktivitat 90

2. Sekretin C. Gewebshormone und verwandte Verbindungen I. Angiotensin Beziehungen zwischen Struktur und Aktivitat 92

2. Kinine , Beziehungen zwischen Struktur und Aktivitat 94

3. Eledoisin und Physalaemin Eledoisin 95. -Beziehungen zwischen Struktur und Aktivitat 96.

-Physalaemin 98

D. Peptidantibiotika I. Gramicidin und verwandte Verbindungen Beziehungen zwischen Struktur und Aktivitat 100

2. Polymyxin Bl und verwandte Verbindungen E. Peptidwirkstoffe mit Depsipeptidstruktur Beziehungen zwischen Struktur und Aktivitat 106

Literaturverzeichnis

ContentsInhaltsveizeichnis

Insulin, Structure, .Synthesis and Biosynthesis of the Hormone. By

ANTHONY C. TRAKATELLIS and GERALDP. SCHWARTZ, Division

of Biochemistry, Brookhaven National Laboratory, Upton, L. I., New

York 120

Abbreviations 121


II. Primary Structure of Insulins 122

III. Splitting of Insulin and Isolation of the A and B Chains. 126

A. Splitting of Insulin with Peroxyacids. , 126

B. Splitting of Insulin by Reduction of its SS Bonds. 126

C. Splitting of Insulin by Oxidative Sulfitolysis 126

IV. Recombination of the Insulin Chains 128

V. Isolation of the Regenerated Hormone from Recombination Mixtures. .131

VI. The Chemical Synthesis o~Insulin 132

A. Synthesis of the Insulin Chains 133

I. Synthesis of the A Chain of Insulin 133a. Sheep Insulin A Chain 133

Synthesis of the A 10-21 dodecapeptide 133. -Synthesis of theA5-9 Pentapeptide Azide 135. -Synthesis of the AI-4 Tetra-peptide Azide 135. -Synthesis of the Sheep Insulin A Chain 135

b. Bovine Insulin A Chain 138) c. Human (Porcine) Insulin A Chain 139

].. Synthesis of the BChain of Insulin 139a. Sheep (Bovine) Insulin BChain 139

Synthesis of the B 10-30 Heneicosapeptide 139. -Final Stepsin the Syntheses of the Sheep (Bovine) B Chain 142

b. Human Insulin BChain 43

B. Combination of the Synthetic Chains and Isolation of the Synthetic

Insulins. ...' !46

VII. Rel~tion of Structure of Insulin to Biological Activity. 49

VIII. Biosynthesis of Insulin 151

References. 152

Makrotetrolide. Von W. KELLER-SCHIERLEIN und H. GERLACH, Labo-

ratorium ftir organische Chemie. Eidgenossische Technische Hochschule.Zurich 161

I. Vorkommen und Isolierung 161

II. Die Konstitution des Nonactins : 163

III. Die Konstitution der Nonactinhomologen. 165

IV. Stereochemie der Makrotetrolide 169

1. Konfiguration der Bausteine : 17°

2. Konfilroration von Nonactin und seinen Homologen 174

I nhal tsverzeichnis ContentsVI

177

181

186

!87

v. Massenspektren der Makrotetrolide. VI. Biologische Wirkung und elektrochemisches Verhalten

Nachtrag Literaturverzeichnis.

Limonoid Bitter Principles. By DAVID L. DREYER, U. S. Dept. of Agri-

culture, Fruit and Vegetable Chemist~y Laboratory, Pasadena, California 19O


II. Structure Determination and Chemistry of Limonoids 192

I. Limonin 192

2. Obacunone, Obacunoic Acid, Nomilin, Deacetylnomilin, 7IX-Obacunol

and Veprisone. 194

3. Deoxylimonin 196

4. Ichangin ;- 196

5. Limonin Diosphenol (Evodol) and Rutaevin 197

6. Flindissol, Turraeanthin,A phanamixin and Melianone. 199

7. ~drelone, Anthothecol, Havanensin-I,7-diacetate, Havanensin-3,7-

diacetate, Havanensin-I,3,7-triacetate, Heudelottin, Hirtin, Deacetyl-

hirtin, Grandifolione, Grandifolione Acetate (Khayanthone), Azadirone,

Azadiradione and Epoxyazadiradione 2O1

8. Gedunin, Dihydrogedunin, 7-Deacetylgedunin, 7-Deacetoxy-7-oxo-

gedunin, 7-Deacetoxy-7-oxodihydro-IX-gedunol, Khivorin, 3-Deacetyl-

khivorin, 7"Deacetylkhivorin, 7-beacetoxy-7-oxokhivorin, 3-Deacetyl-

7-deacetoxy-7-oxokhivorin, II {J-Acetoxygedunin, 6IX, II {J-Diacetoxy-

gedunin, Nyasin, Entandrophragmin and Utilin ~..

9. Andirobin, Deoxyandirobin, Methyl Angolensate, Methyl 6-Hydroxy-

angolensate and Methyl 6-Acetoxyangolensate. IO. Nimbin, Nimbolide and Salannin o..~

I I. Mexicanolide (Substarice B), Carapin, 6-Hydroxycarapin, Swietenolide,

Fissinolide, Khayasin, 3{J-Dihydromexicanolide, Swietenine, 6-Deoxy-

destigloylswietenine Acetate and 6- Deoxy- I 2 {Jacetoxyswietenine

Acetate. 12. Odoratin and.Fraxinenone 13. Limonoids of Unknown Constit~tion III. Conformational Problems in Limonoids. IV. Some Biological Properties of Limorioids V. Botanical Distribution and Chemotaxonomy of Limonoids VI. Tables I. Limonoids Occurring in the Meliaceae 2. Limonoids Occurring in the Rutaceae ; 3. Protolimonoids Occurring in Rutaceae and Meliaceae : 4.. Limonoids of Unknown Structure

?TI)

216

..'\

223

229

23°

231

232

232

234

234

236

237

238

238References

Inhaltsverzeichnis Contehts VII

Proaporphin-Alkaloide. Von K. BERNAUER und W. HOFHEINZ, F. Hoff-

mann-LaRoCheundCo., Basel 245

I. Einleitung , 246

II. Vorkommen der Proaporphin-Alkaloide 247

III. Konstitution und Eigenschaften der Proaporphin-Alkaloide 248

I. Allgemeines , 248

2. Cyclohexadienon-Proaporphine 248a. Allgemeine Eigenschaften 248. -b. D-( + )-Pronuciferin und L-(-)-Pronuciferin 251. -c. D-(+ )-Stepharin 251. -d. D-(+ )-GlazioVin 252.-e. D-( + )-CrotonoSin 253. -f. L-(-)-N-MethylcrotonoSin z54. -

g. L-(-)-Fugapavin (Mecambrin) 254. -h. L-(-)-Orientalinon 254.\ -i. L-(-)-Crotsparin 2~5.

3. Cyclohexenon-Proaporphme 255a. L-( + )-Linearisin 255. -b. L-( + )-Amuronin 256. -c. (+ )-Dihydro-orientalinon 256.

4. Cyclohexenol-Proaporphlne 256a. L-(+)-Amurolin 256. -b. Alkaloid C18H23NO3 256.

5. Cyclohexan()l-Proaporphine 258a. D-( + )-Litsericin 258. -b. L-(-)-Oridin (Oreolin) 258. -c. N-

Methyloridin 259.

IV. Biosynthese der Proaporphin-Alkaloide 260

V. Synthese der Proaporphin-Alkaloide 264

I. Proaporphine durch intramolekulare Phenolkupplung Von 7.4'-Dihy-

droxy-I-benzyl-I,2,3.4-tetrahydroisochin01inen (Weg A) 2642. Proaporphine durch intramolekulare Phen01kupplung Von 7,2'_Di-

hydroXY-I-benzyl-I,2,3.4-tetrahydroisochin01inen (Weg B) 2643. Proaporphine tiber 2,3,8,8a-Tetrahydrocyclopent[ij]-isoChin01in-7(I H)-

one (Weg C) 266

VI. Pharmakologische Eigenschaften 269

Vll. Tabellen 270

I. Nattirliche Proaporphin-Alkaloide 270. -2. Derivate nattirlicher Pro-

aporphin-Alkaloide 275. -3. Synthetische Proaporphine 278.


Chemie der Chlorine und Porphyrine. Von H. H. INHOFFEN, J. W.

BUCHLER und P. J AGER, Institut fiir organische Chemie der Tech-

nischen Hochschule, J,'3raunschwr-ig 284

Einleitung 285

I. AbschluB der Strukturermittlung der Chlorophylle a und b 286

I. Totalsynthese des Chlorophylls a 286a) Der Grundgedanke 286b) Die neue Porphyrin-Synthese 287cl Der Weg vom Porphyrin (IS) zum Chlorin e8-trimethylester 291

2. Die absolute Konfiguration der CWorophylle a und b 294

3 Strells Publikation 295

VIII Inhaltsverzeichnis Contents

II. Bacteriochlorophyll 297/ Weitere Chlorophylle 298

III. Porphyrinsynthesen 298

I. Synthese unsyInrnetrischer Porphyrine. 298

2. Urnbau von Porphyrinen als AbschluB der Synthese natiirlicher Por-

phyrine : 30r

3. Biosynthese 305

IV. Die Bedeutung physikalischer und quantenchernischer Methoden fiirdie

pr§.parative Porphyrinchernie 305I. Physikalische Methoden 305

2. Theoretisch~ Methoden 307

V. Additionsreaktionen arn arornatischen Porphyrinsystern 308

I. Addition v1;)n Wasserstoff 308

a) Allgerneines 308b) Reduktion peripherer Doppelbindungen 309

Einwirkung von Metallen in protonenhaltigern Milieu 309. -Kata-lytische Hydrierung 3r3. -Reduktion rnit Metallhydriden 3I4. -

Reduktion mit Hydrazin und Derivaten 3I4. -PhotochernischeReaktionen 315

c) Reduktion an den Methinbriicken 315Chernische Reduktion 3r5. -Katalytische Hydrierung 316. -

Polarographie und elektrochernische Reduktion 3r6. -Reduktion .in protonenfreien LOsungsmitteln 3r6. -Reduktion in protonen-

haltigen LOsungsmitteln 3r7. -Photochernische Reduktion 317d) Prototrope Urnlagerungen 319e) Dehydrierung 3r9

2. Addition von Sauerstoff 321~) Photo-oxidation der Chlorin-phlorine und Folgereaktionen.. 321b) Hydroxylierung des Porphyrinsysterns 324

3. Addition von Kohlenstoff an Porphyrindoppelbindungen 324

VI. Substitutionsreaktionen 325

I. Elektrophile Substitution 325

a) Deuterierung 327b) Halogenierung 327c) Nitrierung 330d) Acylierung , 33°

2. Nucleophiler Angriff 334

VII. Einfiihrung von Oxofunktionen 335

r. Xanthoporphinogene 335

2. Hydroxyporphine (Oxophlorine) 336

3. Geminiporphyrin-ketone :..337

VIII. Abwandlung von Seitenketten ;..338

I.. Abwandlung der Vinylgruppe 338a) Entfernung der Vinylgruppe 338b) Reduktion der Vinylgruppe 339

c) OxidationderVinvlgruppe ~~Q

\ IXInhaltsverzeichnis -Contents

2. Abwandlung der Formylgruppe 340a) Abspaltung der Formylgruppe 340b) Reduktion der Formylgruppe 34°

3. Reaktionen am iSOCyclischen Fiinfring ,. 340

IX. Zum EinfluB der Zentralmeta11e auf chemische Reaktionen des Porphyrin-

systems. Literaturverzeichnis. : J-.J343

"A~

356

357

358

~67

367

37°

~7I

377

~'7'7

386

392

404

406

408

412

414

Methoden und Ergebnisse der Sequenzanalyse von Ribonucleinsauren.

Von DIETER DUTTING, Max-Planck-Institut fur Virusforschung. Mole-

kularbi010gische Abteilung, Tubingen Abkiirzungen. Symbole. Definitionen I. Einleitung II. Reinigung von Transfer-RN~'s und 5 S-Ribosomaler RNA. I. Transfer-RNA's , 2. Ribosomale RNA III. Analyse von Endgruppen und terminalen Sequenzen IV. Vollstandige enzymatische Spaltung von Ribonucleinsauren und Analyse

der Oligonucleotide. I. Transfer-Ribonucleinsauren a) Spaltweise der Ribonucleasen 377. -b) Trennung der Spaltpro-

dukte 378. -c) Analyse der Oligonucleotide 382.

2. 5 S-RiboSOmale RNA. a) Trennung der Oligonucleotide 386. -b) Analyse der 32p-markierten

Oligonucleotide 389.

3. Quantitative Aspekte der vollstandigen Spaltungen V. Partielle Spaltung von Ribonucleinsauren und Analyse d~r Oligonucleotid-

fragmente I. Partielle enzymatische Spaltung von Transfer-Ribonucleinsauren. a) Partielle Spaltung roit T I-RNase 393. -b) Partielle Spaltung mit

Pankreas-RNase 399. -c) 3'-Terroinale Oligonucleotide in gro(1en

Fragmenten 402.- d) Partielle Spaltung mit der .,sauren" Ribonuclease

aus Milz 403. .

2. Sekundarstruktur von Transfer-Ribonucleinsauren 3. Partielle enzymatische Spaltung von 5 S-Ribosomaler und hochmole-

k)1larer RNA 4. Partielle Spaltung nach chemischer Modifizierung der RNA VI. Schlu(lbemerkungen Literaturverzeichnis. ,

440

Namenverzeichnis. Index of Names

C:~~h..Ar~A;~h...;~ T...~"y nf ~"hi""t_"

Inhaltsverzeichnis

Contents

2

2

3

6

7

12

16

18

18

18

19

21

25

26

?(,

PlaD ScienceEthylene in Nature. EX MARY SPENCER, Department o

The University of Alberta, Edmonton, Alberta, Ca11ada. 31

32

32

33

~~

3435~~

..-

Hochschule, Zurich. Glossaryof Some Cytological, Hist61ogical and Crystallographic Terms. I. Elementary .Fibrils I. Evidence of Subunits in Microfibrils 2. General Occurrence of Elementary Fibrils 3. Crystal Lattice 4. Antiparallelism and Folding of the Cellulose Chains. 5. Crystallinity of the Elementary Fibrils. 6. Function of 1;he Elementary Fibrils in the Cell Wall. II. Biogenesis of Cellulose. I. In vitro polymerization of Cellulose 2. Bacterial Cellulose. 3. Formation of the M-atrix 4. Formation of the Elementary Fibrils 5. GrowthoftheCellWall III. Conclusions. 1?pfpr"nces

2. Analysis Metabolism of Ethylene I. Analytical Problems. 2. Relationships between Ethylene Production and Stages of Physiologica]

1~_~~~+

IV Inhaltsverzeichnis -Contents

b. Ethylene from ,8-Alanine 4°

c. Ethylene from Linolenic Acid; Relationship to Ethane Production 4I

d:Ethylene from Sugars and Krebs. Tricarboxylic Acid Cycle Inter-

mediates. 43

4. Metabolic Fate of Ethylene 44

5. Control of Ethylene Biosynthesis 46

a. Inhibitors and Antagonists 46

Inhibitors Transported from other Parts of the Plant 46. -Carbon

Dioxide 47. -Ethylene Oxide 47.

b. Oxygen Supply. c. Temperature. d. Growth Regulators; Enzyme Synthesis. e. Ageing and Radiation. f. Disease andInjury J.

III. Physiological Activity I. Gross Physiological Effects of Ethylene. a. Plants. ,~

Kinds of Responses 52. -Amounts of Ethylene Required 53.

b. Other Organisms. c. Interrelationships with Effects of Growth Regulators and CO2. ...

2. Mechanisms of Action. a. General Considerations b. Effects on Permeability : ~.

Studies on Whole Organs and Excised Tissues 57. -Experiments

with Mitochondria; Effects of Ethylene on Mitochondrial Adenosine

Triphosphatase 58.

c. Effects on Other Enzymes --

General Criteria 60. -Observed Changes in Enzyme Activity

Concurrent with Changes in Ethylene Production 6I. -Investi-

gations of Possible Effects of Ethylene on Nucleic Acid Metabolism

and Enzyme Formation 6I. -'- Possible Binding to Metal-containing

Enzymes 6I.

d. Possible Basic Mechanisms of Action of Ethylene on Enzymes and

Other Cell Components. The Biological Significance of the Chemistry

of Ethylene. References

48495051OT

52

52"2

53

54

55

55

"7

n()

62

67

81

81

82

91

98

110

121

127

Spectroscopic Methods for Elucidating the Structures of Carotenoids.

By B. C. L. WEEDON, Department of Chemistry. Queen Mary College

(UniversityofLondon), London, E.I I. Introduction. II. Visible and Ultraviolet Light Absorption Spectroscopy. III. Infrared Light Absorption Spectroscopy. IV. Nuclear Magnetic Resonance Spectroscopy. V. Mass Spectrometry : VI. Optical Rotatory Dispersion References. :.

Inha;ltsverzeichnis -Contents v

t"

~

Some Recent Results in the C.hemistry and Stereochemistry of Vitamin D

and Its Isomers. By GEORGINE M. SANDERS, J. POT and E. HA VINGA,

Chemische Laboratoria, Rijksuniversiteit. Leiden. 131

I. Introduction. Structure and ConforInation of (Pre)vitamin D and Some

Isomers 131

A. Structures. : 132a) Suprasterol I 133- -b) Suprasterol III 134- -c) Toxisterol A and

B 134. -d) LINSERT.S compound 135- -e) Lumicalciferol 135

B. Conformations. ; ...135a) Calciferol 136- -b) Tachysterol 136- -c) Precalciferol 139- -

d) 5.7-Diene Steroids 140

II. Photochemical Isomerisations I4I

A- The Calciferol Series 141I.. Reversible Photoisomerisations I4I. -2. Irreversible Photoisomeri-sations; Overirradiation 1..43- -3- Resulting Scheme of Isomerisations

I45B. I3(X-Compounds I48

III. TherInal Isomerisations 148

A. Precalciferol-Calciferol Interconversion I48I- Mechanism 148- -2- Composition of the Equilibrium Mixture I49

B. Isomerisation of Precalciferol into pyrocalciferol and Isopyrocalciferol I5~

IV- Conclusion 152

References. 153

k

~

Konstitution, Entstehung und Bedeutung der Flavonoid-Gerbstoffe.Von K. WEINGES, W. BAHR, W. EBERT, K. GORITZ und H.-D.

MARX, Organisch-chemisches Institut der Universit~t Heidelberg 158

I. Einleitung 159

II. Verwendung und Bedeutung der Flavonoid-Gerbstoffe 163

III. Die Gerbstoffbildner 164

I. Die absolute Konfiguration und die stereochemischen Zusammenhangezwischen Catechinen und Leukoanthocyanidinen 164

2. Die natiirlichen Catechine 169

3. Die natiirlichen Leukoanthocyanidine 178

4. Allgemeiner massenspektrometrischer Zerlall der Catechine und Leuko-

anthocyanidine 197

IV. Die saurekatalysierte Gerbstoffbildung. 201

I. Abhangigkeit der Selbstkondensation Von der Anzahl und der Stellungder Hydroxylgruppen 201

2. Die saurekatalysierte Selbstkondensation des ( + )-Catechins 203a) Isolierung und Konstitution des Dicatechins 203b) Isolierung und Konstitution des Anhydro-dicatechins. 206

C) Konstitution der Catechin-Gerbstoffe 207rl

.TT Tnhaltsverzeichnis Contents

208

209210

211

211

212

213

214

215

217

218

222

222

222

224

224

225

226

228

228

23.0231

232

232

234

234

234

235

235

238

240

243

245

246

3. Die saurekatalysierte Selbstkondensation der Leukoanthocyanidine.

a) Die natiirlichen dimeren und trimeren Leukoanthocyanidine. ...

b) Konstitution der Leukoanthocyanidin-Gerbstoffe ..;. 4. Modellsubstanzen a) Kondensationen mit Phenol b) Kondensationen mit Resorcin c) Kondensationen mit Phloroglucin 5. Reaktionsmechanismus der Kondensationsreaktionen a) Bildungsmechanismus der Catechin-Gerbstoffe b) Bildungsmechanismus der Leukoanthocyanidin-Gerbstoffe 6. Stereochemie der Kondensationsreaktionen V. .GerbstoffbilduY{g durch enzymatische Dehydrierung I. Die oxidative Kupplung einfacher Phenole a) Radikal-Mechanismus b) Radikal-Ionen-Mechanismus c) Ionen-Mechanismus d) Folgereaktionen. 2. Dehydrierung des (+)-Catechins a) 8-Hydroxy-(+)-catechin b) Dehydro-dicatechin A. c) Weitere Dimere und Trimere d) Bildungsmechanismus der Dehydrierungspolymerisate 3. Oxidative Kupplung von Polyphenolen bei der Teefermentierung. ..

a) Theaflavin b)Weitere Bisflavanole VI. Die dimeren Proanthocyanidine ,

I. Vorkommen 2. Allgemeine Vorschrift zur Isolierung der Proanthocyanidine 3. Einteilung 4. CaOH24O12-Procyanidine (GruppeA) 5. CaOH28O12-Procyanidine (GruppeB) ; 6. Andere Proanthocyanidine 7. Biogenese Literaturverzeichnis.

261

262

263

265

265

267267260

Chemie der Wirkstoffe aus dem Fliegenpilz (Amanita muscaria) .

Von C. H. EUGSTER, Organisch-chemisches Institut der Universitat

Zurich. I. Einleitung II. Der Fliegenpilz als zentralaktive Droge III. Isolierung der Wirkstoffe :...

A. Isolierung von quaternaren Ammoniumbasen B. Isolierung von Muscimol, Ibotensaure und Muscazon. I. Die biologischen Testverfahren 2. Isolierung der Wirkstoffe C. Isolierung von (-)-(R)-4-Hydroxypyrrolidon-(2r und weiteren N.

Heterocvclen

VIIInhaltsverzeichnis -Contents

273273

IV. Vorkommen und analytische Nachweise. A. Muscarin B. Vorkommen und analytische Nachweise Von Muscimo1. 'lQotensaure

undMuscaZOn ~ 274

V. 1Jbersicht iiber weitere Inhaltsstoffe des Fliegenpilzes 276

A. Farbstoffe der Huthaut (,.Muscarufin..) : 276

B. Andere Inhaltsstoffe 277

VI. Chemie ausgewahlter Stoffe aus A. musca'.ia. 279

A. ..Muscaridin" )lnd Butenylammoniumsalz. , 279

B. Muscarin. Stereo- und Strukturisomere 280

I. Neue Synthesen von Muscarin und Stereoisomeren 281

2. Synthesen von strukturisomeren Muscarinen 286

3. Racematspaltungen 287

4. IR- und NMR-Spektren stereoisomerer Muscarine. 288

5. Dehydromuscarine 288

6. Synthesen von Musc~rinhom010gen und -analogen 291

7. Thiomuscarine 293

8. Oxamuscarine (quatecnare I.3-DioX01anverbindungen) 295

C. Muscim01 ; 299

I. Struktur, Reaktionen 299

2. Synthesen von Muscim01 und Hom010gen 300

D. Ibotensaure 303

I. Struktur und Reaktionen 303

2. Synthesen 305

E. Muscazon 308

I. Struktur und Reaktionen 308

2. SynthesedesMuscazons 310

VII. Biogenese der Wirkstoffe 311

A. Muscarin und verwandte Verbindungen 311

B. Ibotensaure, Muscazon und 4-HydroXypyrr01idon 312

VIII. Hinweis auf die Pharmak010gie der Ibotensaure und des Muscim01s. 3I4


~

322

322

323

323

325

328

330

330

333

334

334

:i:i~

j

The Chemistry of Sorl;1e Toxins Isolated from Marine Organisms.

By P. J. SCHEUER, Department of Chemistry, University of Hawaii,

Honolulu, Hawaii I. Introduction. II. Toxins Isolated from Chordates I. Tetrodotoxin 2. Pahutoxin 3. Ciguatoxin III. Toxins Isolated from Echinoderms I. The Holothurins 2. The Asterosaponins IV. Toxins Isolated from Mollusks I. Saxitoxin 2. The Aplvsins

-J

VIII Inhaltsverzeichnis -Contents

v. Toxins Isolated from Coelenterates

Palytoxin VI. Toxins Isolated from Protozoans .

Prymnesin VII. Conclusion References.

: : : : : : : : : : : 335

335

336

336

336

336

340

341

341

342342343344346346347

348348351351352352357

358358359359359360

361361363363365

36636636937037°371373

374

The Chemistry of Lysozyme. By M. A. RAFTERY and F. W. DAHL-

QUIST, California Institute of Technology, Pasadena, California. I. Introduction II. General Properties of Lysozyme III. The Chemical Structure of Lysozyme I. Primary Structure 2. Secondary Structure. 3. Crystal Structure. "; 4. Other Studies of the Tertiary Structure. a) Titration Data b) Hydrogen Exchange IV. The Binding of Inhibitors and Substrates to Lysozyme I. X-ray Methods. 2. U. V. Spectroscopic and Fluorescence Methods. a) Chitin Oligosaccharides. b) Cell Wall Oligosaccharides 3. Nuclear Magnetic Resonance Methods 4. Rates of Complex Formation and Dissociation. V. Chemical Modificationof Lysozyme I. Tryptophan Residues. 2.. Histidine Residues. 3. Lysine Residues. 4. Tyrosine Residues 5. Carboxyl Groups. VI. Oligosaccharide Substrates for Lysozyme. I. Oligosaccharides of NAG 2. CellWall Ol.igosaccharides 3. Enzymatic Synthesis of Mixed Oligosaccharides 4. Aryl Glycosides as Synthetic Substrates. VII. The Mechanism of Lysozyme Catalysis I. Glycosyl Carbonium Ions 2. Nucleophilic Catalysis. 3. Experimental Evidence for the Catalytic Mechanism of Lysozyme. ...

a) Product Analysis. b) Investigation of Rate Determining Steps. 4. Discussion References.

382

397

Namenve~zeichnis. Author Index

S""hverzei"hnis. Subiect Index. .

lnhaltsverzeichnis

Contents

Structural and Biogenetic Relationships of Isoflavonoids. By E. WONG.Applied Biochei:nistry Division, Pal.merston North, New Zealand. 1

I. Introduction 2

II. Isoflavones 4

I. Simple Isoflavones 52. Complex Isoflavones 93. Isoflavone Glycosides 44. Synthesis of Isoflavones 17

III. Isoflavanones 19

IV. Rotenoids 22

.V. Pterocarpans 25

1. Natural Pterocarpans 262. Stereochemistry of Pterocarpans 303. Reactions and Synthesis of Pterocarpans 31

VI. Isoflavans. 33

VII. 3-Aryl-4-hydroxycoumarins 36

1. Structure Elucidation 382. Synthesis of 3-Aryl-4-hydroxycoumarins 40

VIII. Coumestans 41

1. Natural Coumestans 412. Structure Elucidation and Synthesis. 43

IX. Other Types of .Isoflavonoids 45

X. Biogenesis of Isoflavonoids 46

1. 1,2-Aryl Migration as a Common Feature. 482. Branching Point from the Flavonoid Pathway. .., 493. Nature of the Primary Isoflavonoid Product. 514. Biogenetic Relationships among the Isoflavonoid Classes. 53

a) Direct Experimental Evidence 53b) Co-occurrence of Class~s of Isoflavonoids 54c) Isoflavanones -Dehydropterocarpans -Pterocarpans -Isofla-

vans -Coumestans 55d) Isoflavones -2-Hydroxyisoflavones -3-Aryl-4-hydroxycoumarins 58e) Isoflavones -Rotenoids -Coumaronochromones. ., 59f) Summary of Biogenetic Interrelationships. 61

References. 6~

lnhaJtsverzeichnis -ContentsVI

75

Recent Advances in the Chemistry of Cyanogenic Glycosides. By R.

EyJOLFSSON, The Royal Danish School of Pharruacy, Chemical Labo-

ratoryB, Copenhagen, Denmark I. Introduction II. General Chemical Considera-tions Structural Relationships 75. -Chemical Properties 80. -Enzymic

Degradation 81.

III. Detection , Detection in Fresh Plant Specimens 82. -Detc:;ction on Chromato-

grams 83.

IV. Isolation. ..:. ; Column Chromatography 84. -Preparative Paper Cnromatography 85

-Preparative Thin Layer Chromatography 85. -Gas Liquid chro-

matography 85.

V. Structure Elucidation Gynocardin 85..~ Triglochinin 87. -Dhurrin and Taxiphyllin 89. -

Linamarin 90. c- Lotaustralirl 91. -Proteacin 91. -Nandina-

glucoside 92.

VI. Synthesis VII. Distribution. Cyanogenesis ill Higher Plants 95. -Cyanogenesis in Bacteria 95. ...:

Cyanogenesis in Fungi 95. -Cyanogenesis in Animals 95.

~

VIII. Biosynthe;is : IX. Metabolic Aspects The Fate of Cyanogenic Glycosides in Living Organisms 100.. -vy~li.U'

Metabolism 100.

82

84

85

92

(16

100r..~~;A~

IO3References

Naturstoffe mit Pyridinstruktur und ihre Biosynthese. Von D. GROSS,Institut fiir Biochemie der Pflanzen, Halle (Saale).. Weinberg,D lli( IO9

IO9

IIO

113

113

115

115121

r24

12.S

Einftihrung I. Nattiriich vorkoromende Pyridinverbindungen

1. Carbonsauren und einfache Pyridinderivate

2. Alkaloide ,

a) Nicotin und verwandte Alkaloide b) Pyridonalkaloide c) Terpenoide Alkaloide d) Verschiedenartige Pyridinalkaloide 3. Aminosauren mit Pyridinstruktur 4. Mikrobielle Stoffwechselprodukte

VIIInhaltsverzeichnis ~ Contents

II. Biosynthese des Pyridintinges 126

1. Entstehung der Nicotinsaure 127a) Oxydativer Tryptophanabbau 127b) C3-+C4-Kondensation 129C) PYJ:"idinnucl.eotid-Cyclus 132

2. Biosynthese Von Fusarinsaure und 2,6-Dipico1insaure 1353. Lysin als pyridinvorstufe : 137

a) Biosynthese Von Mimosin ~wie Desmosin und Isodesmosin. 137b) In vitro-Biosynthese von A:nabasin 139

4. Entstehung des Pyridinringes auf dem.Monoterpenweg 1405. Biosynthese der PiericidineA undB 144

III. Hypothesen zur Biogenese weiterer Pyridinverbindungen... 144

SchluBbetrachtung 145


,

Peptide Alkaloids. By E. W. WARNHOFF, Department of Chemistry,University of Western Ontario, London, Canada. I62

I. Introduction ,. I63

II. General Properties of Peptide Alkaloids. I64

III. General Methods and Techniques of Structural Determihation I65

IV. Structure and Properties of Peptide Alkaloids. 167I. Pandamine I672. Zizyphine. I7°3.. Ceanothine.B I724. Scutianine I755. Integerrine I176. Lunafine 1797. Homaline r8I

8. Adouetine-X 1839. Americine I83

10. Aralionine 184I I. Ceanothine.:A : 184

12. Franganine.. Frangufoline, and Frangulanine , 185

I3" Hymenocardine I85I4. Integerrenine.and Integerressine I86I5. LBX and LBZ I86

I.6. Lasiodine-A .; I.87

V. Ultraviolet Spectra of Peptide Alkaloids I87

VI.. NMR Spectra of Peptide Alkaloids 190

VII. Mass Spectra of Aryloxy Macrocyclic Peptide Alkaloids. I9I

VlII. Pharmacological Properties oi Peptide Alkaloids I93

IX. Tables .I93I. BasicityofPeptideAlkaloids 1932. Peptide Alkaloids. : ; i943. Sources of Peptide Alkaloids 200

References. : 20I


Insektensexuallockstoffe. Von K. EITER, Bayerwerke Leverkusen,

Koln-Stammheim, BRD I. Einleitung II. Insektensexuallockstoffe a) Olefinische Verbindungen b) Aliphatische Verbindungen " c) Terpenartige Verbindungen d) Heterocyclische Verbindungep III. Weitere Pheromone IV. Insektenhormone a) Juvenilhormon (JH) b) Hl1utungshormon (MH = moulting-Hormon) c) Sterilisanti~n (Juvenilhormonartige Substanzen)

d) Synthetische Produkte : LiteraturverzeichniB.

204

204

206206

237237244

246

246246248249249

250

ArthropodMoltingHormones. By HIROSHI HI~INO and Y ASUKO HIKINO,Pharmaceutical Institute, Tohoku University, Aoba-yama. Sendai,

Japan 256

I. Introduction 257

n. Hormonal Regulation of Growth of Insects and Crustaceans. 257

III. Occurrence in Animals 258

IV. Occurrencein Plants 261

Y. Isolation and Assay. 263

VI. Structure Determination and Chemistry 264

I. (X-Ecdysone (Ecdysone) , 2642. fJ-Ecdysone (Crustecdysone, 2o-Hydroxyecdysone, Ecdysterone) ...2663. Tobacco Homworm EcdysoneIII (20,26-Dihydroxyecdysone) 2674. Deoxycrustecdysone , 2685. Ponasterone A 2686. PonasteroneB 2727. Ponasterone C 2728. rnOkosterOne. '. 273

9. Cyasterone, Isocyasterone, SengosteroneandCapitasterone. 27410. Polypodine B 275II. Rubrost.erone 27612. PonasterosideA 27613. Shidasterone 27714. AjugasteroneC ~ 27815. Pt.erosterone., Makisterone A, Makisterone B, Lemmasterone (Maki-

sterone C, Podecdysone A), Amarasterone A, Makisterone D andAmarasteroneB , 278

16. Viticosterone E, St.achysterone C, Stachysterone A. St-achysterone B,Podecdysone Band Stachyst.erone D 279

17. Aiugasterone B 280

IXInhaltsverzeichnis -Contents

280

280286289

291

295295296297301303304

305

VII. Synthesis. I. (¥-Ecdysone 2. f3-Ecdysone and Ponasterone A. 3. Rubrosterone 4. Miscellaneous. VIII. Biosynthesis and Catabolism. IX. Tables. I. Animals Known to Contain EcdYSterol!!-

2. Plant Families Containing E{;dysterols .

3. Plants Known to Contain Ecdysterols. .

4. Properties of Ecdysterol~ ..., 5. NMR Data of some Ecdysterols .

6. ORD and CD pata ofEcdysterQls References.

Total Synthesis of Prostaglandins. By J. E. PIKE, Expt;rimental ChemistryDivision, The Upjohn C=pany, Kalamazoo, Michigan, USA. 313

I. Introduction 313

II. Structure and Chemical Transforniations ot the Prostaglandins. 314

III. General Approaches to Prostaglandin Synthesis. 316

A. Initial Corey. Synthesis of dl-PGE1 316B; Corey's Second Synthesis of dl-PGE1 3t9C. A Stereocontrolled Synthesis of Prostaglandins E2 and F2tX (COREY) 322D; Bicyclohexane .Route to Prostaglandins. 324E. Non-EnzymicCyclization of Fatty Acids 33°

IV. Synthetic Routes to Structurally Simplified Prostaglandins. 331A. Synthesis of dl-I3j4cDihydro-PGE1' Ethyl Ester. 331B:Synthesis of dl-I5-Dehydro-PGEi 331C. Synthesisofdl-PGB1 ; 332

V. Synthetic Route~ to Prostaglandin Analogs. 334

A. II-Deoxy-Prostaglandins 334B. 7-0xa-Prostaglandins 335

VI. Miscellaneous Synthetic Approaches. 336

vn. Resolution of Racemic Prostaglandins. 339

References 339

343

344

345

345346349351

Chemistry of Cephalosporin Antibiotics. By R. B. MORIN and B. G .

JACKSON, The University of Wisconsin, School of Pharmacy,Pharmacy

Building, Madison, Wisconsin, USA I. Introduction II. Isolation and Structure of Cephalosporin Antibiotics.. A. Historical B.. Cephalosporin. P C. Cephalosporin N {Penicillin N) : D. Cephalosporin C

x Inhaltsverzeichni~ rnnt"ntR

355355

355355359

360

36636636636836936937°373373375376

377

379

379

389

~Q~

III. Chemical Transformations of CeBhalosporin C A. Nomenclatur.e B. Sidechain Amido Functions. I. Reactions of the 7.(X Aminoadipamoyl Group

2. Reactions of the 7-Amino Group. C. Reactions of the .B-Lactam Ring System. D. Reactions of the Dihydrothiazine Ring System

I. Reactions of the Double Bond. a) Formation of A8-Isomers b) Other Reactions of the Double Bond. ...

2. Reactions of the C-3 Substituents. a) Formation of Desacetyl Derivatives. b) Nucl~ophilic Displacement of the Acetate.

c) Hydrogenolysis of the Acetate. 3. Reactions of the Carboxyl Group 4. Formation of Sulfoxides E. Conformation of Ce1'halosporanates. IV. Physicochemical Properties of Cephalosporanates. ..

V. Syntheses of Cephalosporins A. Total Synthesis. B. Partial Synthesis VI. Biosynthesis. VII. Biological Activity of Cephalosporanates References ..

~Q'

4°4

406.~"

.Tn

Oligosaccharide der Frauenmilch. Von H. WIEGANDT und H. EGGE,

Institut fiir Physiologische Chemie. Universit!t Marburg, Marburg/Lahn,

BRD I. Einleitung II. Isolierung und Analyse der Oligosaccharide. I. Isolierung 2. Analytische Methoden. III. Beschreibung der Zucker IV. Vergleich der freien Kohlenhydrate der Milch und des Urins mit den kon-

jugierten Oligosacchariden der Glykosphingolipide V. Biosynthese und Blutgruppenmerkmale. Literaturverzei"hni" 418

419

Ac22

Glucagon: Chemistry and Action. By W. BROMER, The Lilly Rese.a.rclLaboratories, Eli Lilly and Company, Indianapolis, Indiana, USA. .

T Tntrnn"f'tinn

II. A430

..'00,~1 l\K~.h~..~

Inhaltsverzeichnis -Contents XI

2. Bioassay. 430a) Measurement of the Hyperglycemic Action,of Glucagon. 430b) MeasurerneRt of thc Glycogenolytic Effect of Glucagon. 431

3. Radioimmune Assays ' 431,

III. Chemical Aspects. 432

I. Isolation, Properties, and Primary Structure. 4322. Synthesis. 4353. Conformation. 4354. Relationships of Structure and Function. 437

-

IV. Site of Formation and Release 438

I. Pancreas. 4382. Intestine. 4393. Release 440

V. Glucagon in Blood. 440

I. Concentration. 4402. Catabolism. 441

VI. Glucagon Action 441

I. On Adenyl Cyclase 4412. In Pancreatic p-cells 4423. In Liver 4434. In Adipose Tissue. 4445 In Heart 4446.In the Gastrointestinal System c4457. On Plasma Electrolytes and Renal Function. 445

VII. Physiologic Role. 446

References. 446

Namenverzeichnis. Author Index... ... 453

Sachverzeichnis. Subject Index. .. 474

,1

Inhaltsverzeichnis

Contents

Vorkommen, Struktur und Biosynthese natiirlicher Piperidinverbin-

dungen. Von D. GROSS, Institut fiir Biochemie der Pflanzen. Deut-sche Akademie de; Wissenschaften. Halle (Saale). Weinberg. DDR I

Einfiihrung 2

I. Einfache Piperidinderivate 3I. Piperidin und Methylpiperidine 32. Piperidin- und Piperideincarbonsauren. 43. Biosynthese der Pipeco1insaure 6

n. Aliphatisch substituierte Piperidinbasen 8I. N-Substituierte Piperidine (Piper-Alkaloide). 82. cx-Substituierte Piperidine 9

a) Conium-Alkaloide ,. 9b) Punica-Alkaloide I2c) Strukturahnliche Sedum-. Lobelia- und Haloxylon-Basen. I4d) Withania-Alkaloide , I6e) Febrifugin und Isofebrifugin 17f) Nigrifactin. 18

III. Aliphatisch cx.1X'-disubstituierte Piperidine. I8I. Pinidin I82. Lobelia- und Sedum-Alkaloide , 193. Cassia- und ProsoPis-Alkaloide 224. Caria- und Azima-Alkaloide 23

5. Lythraceen-Alkaloide 24

IV. Heterocyclisch substituierte Piperidine. 24I. Anabasin- und Te~rahydroanabasinalkaloide. 242. Lobinalin 293. Ormosia-Alkaloide 3I4. Lampro1obin. Aphyllinsauremethylester und Leontiformin 31

5. Nuphar.:Alkaloide 326. Piperidinhaltige Indo1alkaloide (Secamine. Secodine und Nitrarin) 33

(V. Monoterpenoide Plperidinalka10ide 34

, ,VI. Verschiedenartige Piperidinstrukturen 36

I. Alkaloide 362. Betalaine 383. Antibiotica 40

VII. SchluBbetrachtung : 41


InhaltsverzeichnisIV Contents

Gallenfarbstoffe und Biliproteide. Von W. R UDIGER, Botanisches Insti.tut der Universitat Miinchen, BRD ~... ..: 60

61

62

64

64646666

68697n

73

73767984

89

9091

94

9499

104

10410410R

I. Einleitung. , ...

II. Nomenklatur III. Chemische Untersuchungsmethoden I. Farbreaktionen ~ Die Gmelin-Reaktion und ihre Erweiterung Die Jaffe-Schlesinger-Reaktion und ihre Erweiterung

Die Diazoreaktion 2. Abbaure\1.ktion.en Abbau mitPermanganat Abbau mit Chromsaure und Chromat IV. Physikalische Untersuchungsmethoden I. Elektronenspektren...~ 2. Optische Aktivitat 3. Massenspektren 4. NMR-Spektren 5. Chromatographie V. Bilirubin. I. Bilirubin-Konjugate 2. Bilirubin-Proteide VI. Umwandlungsprodukte des Bilirubins I. Bilane und Bilene-(b) (U'.obilinoide) ,

2. Biladien~-(a.b) VII. Bilatriene I. Biliverdin und Mesobiliverdin 2. Biliverdin und Biliverdin-Proteide bei Vertebraten .

3. Bilatriene bei Invertebraten VIII. Gallenfarbstoffe mit Athylidengruppe I. Aplysia-Farbstoffe 2. Phycobiliproteide Phycobiline 3. Phytochrom Literat1\rverzeichnis.

III

III

114118

124

12R

The Chemistry of Glutarimide Antibiotics. By F. JOHNSON, The DowChemical Company, Eastern Research Laboratory. Wayland, Massachu-setts. USA

I. Introduction. II. The Chemistry of the Glutarimide Antibiotics

I. Nomenclature 2. Isolation and Determination.

Inhaltsverzeichnis Contents v

3. The Structure of Cycloheximide and Its Isomers I46a) The GroSS Structures of Cycloheximide, Isocycloheximide and

Naramycin-B :' 146b) Absolute Configuration 151c).Fine Structure I52d) Miscellaneous Chemistry I68

4. The Streptovitacins and E-73 I745. Inactone :. I796. Actipheno1 (C-73) 1807. Streptimidone and Protomycin : I818. Fermicidin, Niromycin-A and Niromycin-B I86

III. Synthesis I86

I. Cycloheximide, Naramycin-B and Isocycloheximide 1872. lX-Epiisocycloheximjde I9I

3. Actipheno1 I934. Homo1ogs and Analogs of Cycloheximide and Other Related Substances I93

IV. Biosynthesis. I97

References 202

Chemie und Biosynthese der Flechtenstoffe. Von S. HUNECK, Institutfiir Biochemie der Pflanzen. Deutsche Akademie der Wissenschaften.Hal1e (Saale). Weinberg. DDR 2og

I. Einleitung. 209

II. Methoden zum Nachweis und zur Strukturaufklarung der Flechtenstoffe 210

A. Dilnnschichtchromatographie 210B. Papierchromatographie 211C. Gaschromatographie 211D. InfrarotSpektroskopie 211E. Ultravi01ettspektroskopie 211F. NMR-Spektroskopie 212G. Massenspektrometrie 213H. Rontgenstrukturanalyse 215I. Chemische Methoden 215

III. Einteilung der Fleclitenstoffe 216

IV. Strukturaufk1arung und Synthese der Flechtenstoffe 216

I. Produkte des Primarstoffwechsels 2162. Acetogenine 220

3. Phenylalanin-Derivate 2694. Vitamine 273

5. Enzyme. , 273

V. Biosynthese der Flechtenstoffe 273

VI. Aus Mycobionten is01ierte Verbindungen 285

VII. Chemotaxonomie der Flechten : 285

VIII. Antibiotische und weitere bi010gische Wirkungen der Flechtenstoffe. .287L.t t . h ."" 1 era urverzelC nl". ~

v Inhaltsverzeichnis -Contents

The Cucurbitanes, a Group of Tetracyclic Triterpenes. By D. LAVIE

307

~O8

~O9

310

311

'ill

311

312

313

314

316

317

322

323

325

3.25

329

329

332

334

336

~~7

337

338

339

339

341

341

341

342

343

346

2.11

I. Introduction. II. The Carbon Slreleton up to 1960 III. Nomenclature. IV. Structure Determination and Chemistry of Cucurbitacins. I. Cucurbitacins B, D, E and I ,

1.1. Interrelationship Between Cucurbitacins B (5), D (Elatericin A)

(6), E (Elaterin) (2) and I (Elatericin B) (7) 1.2. The Skeleton. 1.3. The Side Chain. 1.4. The Ring A Substituents; the cx-Hydroxy-ketone (5), (6) and the

Diosphenols (Enor1Zed cx-Diketone) (2), (7) 1.5. The 19-Methyl Group and Ring C Carbonyl. 1.6. The RingB Double Bond 1.7. The 16-Hydroxy Group 1.8. The Alkaline Treatment of Elaterin 2. Cuc~rbitacins A (61) and C (69) 2.1. Structure Determination 2.2. Interrelationship Between Cucurbitacins A, Band C 3. Stereochemistry of Cucurbitacins 4. Stereochemistry.of Ring A Keto.ls 5. Interrelationship Between the Cucurbitane and Lanostane Series 6. Synthesis of a 32-nor-Cucurbitane Skeleton. V. Cucurbitacihs G, H. L, J, K, Dihydrocucurbitacin Band 22-Deoxo-

cucurbitacin D I. Cucurbitacins G and H (108) 2. Cucurbitacins J, K (109) and L (110) 3. Dihydrocucurbitacin B (III) 4. 22-Deoxocucurbitacin D (112) 5. "t1-Elaterin" ...; VI. Isocucutbitacin B (119). 22-Deoxoisocucurbitacin D (120) and Tetra-

hydrocucurbitacin 1{121) I. Isocucurbitacin B (119) 2. 22-DeoxoisocucurbitacinD.(I20) 3. Tetrahydrocucurbitacin 1(121) VII,. Bryodulcosigenin (123), Bryosigenin (124), Bryogenin (125), Gratiogenin

(126) and I6-Hydroxygratiogenin(I27) : VIII. Cucurbitacin F (I34a), O (I35a). p (I36a), and Q (I37a) IX. Cucurbitacins of Unknown Structure.

and E. GLOTTER. Department opChemistry, The Weizmann Instituteof Science, Rehovot. Israel.

Inhaltsverzeichnis -Contents VII

348

350

351

352

352356

3'57

x. Biogenetic Aspects. , "'

XI. Ph y sical Methods in the Structure Elucidation of the Cucurbitacins

, "'

XII. Biological Properties of the Cucurbitacins :'.. ..

XIII. Tables. , , I. Occurrence of the Cucurbitacins in Nature. 2. Physical Constants of the Cucurbitacins References.

Biogenetic-type Synthesis of Terpenoid Systems. By D. GOLDSMITH,Department of Chemistry, Emory University, Atlanta, Georgia, USA 363

Introduction. 363

I. Th~ory of Polyene Cyclization 364

ll. Acid Catalyzed Cyclization : 366

III. Oxidative Cyclization 369

IV. Arene and Alkyl Sulfonates, Acetals and Allylic Alcohols. 378

V. Cyclopropyl Ketones, Enols, and Tertiary Alcohols. 384

VI. Carbonium Ion Catalyzed Cyclization 390

Vll. Radical Cyclization 390

References 391

395

395

396

397399401403

403

403406

412

413

The Biosynthesis of the Diterpenes. By J. R. HANSON, Chemical Labo-

Chemistry of Natural Products Derived from Marine Sources. By E.PREMUZIC, World Life Research Institute, Colton, California, USA 417

I. Introduction , 417

II. Steroids " 418III. SaDo~enins of Marine Ori~in "2.;

ratory. The Unjve~sity of slissex. Falmer, Brighton. England. I. Introduction. .II. The Biogenesis of the Diterpenes I. The Bicyclic Diterpenes 2. The Tricyclic Diterpenes ; 3. The Tetracyclic Diterpenes 4. The Macrocyclic Diterpenes III. Biosynthetic Evidence. I. The Bi- and Tricyclic Diterpenes 2. The Tetracyclic Diterpenes IV. Conclusion. References.


431

435

446

451

460

467

469469

472

IV. Bile Alcohols and Bile ~cids V. Terpeiles and Related Hydrocarbons.. VI. Halogen-Containing Compounds. VII. Non-Proteinoid Nitrogen-Containing Substances

VIII. Quinonoid andRelated Pigments. IX. Carbohydrates X. Related Topics. Addendum. References ..

Namenverzeichnis. Author Index48q

Sachverzeichnis. Subject Index

Inhaltsverzeichnis

Contents

1

2

5

5

6

8

14

Bioluminescence: Chemical Aspects. By M. J. CORMIER, J. E. WAMPLER, and K. HORI,

Department of Biochelpistry, University of Georgia, Athens, Georgia, USA ...

I. Introduction II. Renilla(SeaPansy)Bioluminescence 1. General Comments. 2. ChemicalRequirementsforLightEmission 3. MechanismoftheLightRea~tion 4. RelatedBioluminescentSystems

16161720

26262628

3~

33333435

41414142

444445

47

53

rn. FireflyBioluminescence 1. GeneralComments 2. Chemical Requirements for Light Emission. 3. MechanismoftheLightReaction , i

IV. CypridinaBioluminescence 1. GeneralComments 2. Chemical Requirements for Light Emission. 3. Mechanism of the Luminescent Reaction. 4. RelatedBioluminescentSystems V. BacterialBioluminescence 1. GeneralComments 2. Chemical Requirements for the Light Reaction. 3. MechanismoftheLightReaction VI. Latia Bioluminescence. 1. Genera[Comments 2. Chemical Requirements for Light Emission. 3. MechanismoftheLightReaction VII. EarthwormBioluminescence 1. GeneralComments 2. Chemical Requirements for Light Emission. vrn. Comments on General Mechanisms Involved in Bioluminescence

References.

Gametenlockstoffe bei niederen Pflanzen und Tieren. VonL. JAENICKE und D. G. MUL.

LER, Institut fiir Biochemie der Universitat Koln, BRD ". I.Einleitung , II. Verbreitung der Gameten-Lockstolfe

fi4

Tnh"It.."verzeichnis ContentsTV

65

65

66

6666676970

76

7676788081

81

88

88899092

93

96

III. Spezifitiit chemotaktisch wirksamer Substanzen IV. Topo- und phobotaktische Reaktion ..:. V. Sirenin a) Vorkommen, Funktion und Bestimmung b) Isolierung ; ,...

c) Strukturaufkliirung d) Biosynthese e) Total-Synthesen von Sirenin VI. Ectocarpen a) VorkommenundWirkung b) Gewinnung und Nachweis c) Strukturbeweis d) Synthese e) Biosynthese VII. Dictyopteren und andere Inha1tsstoffe von Dictyopteris VIII. Einige weitere Fiille von Gameten-Chemotaxis a)Fucus b) Chlamydomonas c) Sphaerocarpos ' d) Campanulariacalceolifera IX. Betrachtungen zum Wirkungsmechanismus der Gametenlockstoffe

T..it.erat.urverzeichni~

Quassinoid Bitter Principles. By JUDITH POLONSKY, lnstitut de Chimie des SubstancesNaturelles. Centre Nationale de la Recherche Scientifique, Gif-sur- Yvette, France . 10.\

102

104

106

108

109

IOQ

115

115

120

124

I. Introduction. II. Quassinoid General Features. I. Chemical Properties. 2. Spectral Properties : III. Structure Determination ofQuassinoids I. Quassin and Neoquassin 2. Nigakilactones A, B, C, E, F, H, Simalikalactone C, Picrasin D, E and F, and

Nigakihemiacetals A and C 3. Amarolide, ll-Acetylamarolide, Chaparrolide, Castelanolide, Klaineanone, 11-

Dehydroklaineanone, 15-Hydroxyklaineanone, Picrasin B, and 6-Hydroxy-

picrasin B, Picrasin C 4. Glaucarubin, Glaucarubinone, Glaucarubol, Glaucarubolone, 15-Isovaleryl-

glaucarubol, 15-Acetoxyglaucarubolone (Holocanthone), a-Methyl-a-acetqxy-

butyric Ester of Glaucarubolone, Ailanthinone 5. Chaparrin, Chaparrinone, and Ailanthone I; Rn,cein,A-G.Brusatol.andSimalikalactoneD

lnhaltsverzeichnis Contents v

128

129

131

138

140

142

142

146

146

, .'7

7. Samaderins B, C and D, 3,4-Dihydrosamaderin B"Cedronin, Cedronolin, and

Eurycomalactone 8. Simarolideand Picrasin A (=Nigakilactone G). IV. The Biogenetic Isoprene Rule and the Biosynthesis ofthe Quassinoids V. Tetracyclic Triterpenes from Simaroubaceae VI. Physiological Activity. '. VII. Tables. I. Quassinoids ofType A 2. Quassinoids of Type B 3. Quassinoids of Type C References.

Die Ergochrome (Physiologie, Isolierung, Struktur und Biosynthese). Yon B. FRANCKund H. FLASCH, Organisch-Chemische~ lnstitut der Universitiit Miinster, BRD .. 151

1>2

153

153

156

157

157

157

159

I"a

163

163

163

1661.'1

176

177

178

180

186

187

190

192.

192

193

200

20)

I.Einleitung II. Al1gemeineInfonnationeniiberErgochrome 1. Strukturvariation und Nomenklatur der Ergochrysine A und B 2. IsolierungundTrennungderErgochrome a) Aus Mutterkom b) AusFlechten c) Aus Schimmelpiizen d) Obersicht iiber das Vorkommen der Ergochrome e) Trennungsmethoden 3. BiologischeAktivitiitderErgochrome III. Struktur und Konfiguration der Ergochrome 1. Met'hodenzurStrukturbestimmung a) DasaromatischeGrundgeriist b) Struktur von Ring C c) VerkniipfungderMolekiilhiilften 2. Methoden zur Konfigurationsbestimmung und Struktur der Secalonsiiuren A

BundDsowiedesErgoflavins :.

a) Konfiguration der C-Methylgruppe an C-6 b) Konfiguration der sekundiiren Hydroxygruppe an C-5 c) Konfiguration am Ringverkniipfungszentrum C-I0 3. Struktur der Secalonsiiure C sowie der Ergochrysine A und B 4. Strukturen der Ergochrome AD. BD, CD und DD. 5. Strukturdes Ergoxanthins : IV. BiosynthesederErgochrome 1. Hypothesen 2. Fiitterungsversuche 3. Model1reaktionen Literaturverzeichnis

lnhaltsverzeichnis Cnnt.ent."

The Chemistry of Biflavanoid CQmpounds. By H. D. LOCKSLEY, Department of Che.

mistry.UniversityofSalford.En~land. 207

I. Introduction. : 208

II.NomenclatureforBiflavanoids 211

I~I. Chemistry of Biflavones of the Amentoflavone (1) Family-Structures of Ginkgetin

(13), Isoginkgetin (23), and Sciadopitysin (14) 212

IV.BiflavonesoftheHinokiflavone(2)Family 226

V. Biflavones of the Cupressuflavone (3) Family. 234

VI. Biflavones of the Agathisflavone (4) Family. 237

VII. Methods for the Location of O-Methyl Groups in Biflavones 240

VIII. Chiral Properties of Biflavones 252

IX.. Reduced FormsofAmentoflavone and Hinokiflavone 253

X. The C-3/C-8 Biflavanones 260

XI. Flavanone-f1avones Possessing a C-3/C-8 Interflavanoid Linkage. 275

XII.NaturalGlycosidesofBiflavanoids 283

XIII. SynthesisofBiflavanoids 285

I. Ullmann Coupling of Flavones 285

2.. Ullmann Synthesis of Biflavones via Biphenyl Precursors. 289

3.Wesseley-MoserRearrangements , 292

4. Partial Demethylation and Methylation of Natural and Synthetic Biflavones 292

5. Phenol Oxidative Coupling of Flavones as a Route to Biflavones 295

XI.y.Pharmacology 298

XV. Tables. 299

I..BiflavonesoftheAmentoflavoneSeries 299

2.BiflavonesoftheHinokiflavoneSeries 299

3. Biflavones of the Cupressuflavone Series. 300

4.BiflavonesoftheAgathisflavoneSeries 301

5. Natural Distribution of Biflavanoids 301

6. 1 H NMR Spectral Data for Biflavanones (9Hl2) 304

7. Optical Rotatory Dispersion Data for Biflavanones (9)--(12) 305

Ref ere nce s 305

A dden dum 311

Chemie der Makrolid-Antibiotica. Von W. KELLER-SCHIERLEIN, Organisch-Chemisches

Laboratorium, Eidgen6ssische Technische Hochschule, Zurich, Schweiz 313

I. Einleitung : : 314

II. Antibakterielle Makrolid-Glvkoside aus Actinomvceten 315

VIIContentsInhaltsverzeichnis

316316327333

336337358

360

360

364365377

383

384384385394

396

397

410

413

413414421

425

432

.434

.443

.444

.445

1. Die Erythromycin-Gruppe a) DieKonstitutiondesErythromycins b) Konfiguration und Konformation des Erythromycins. ,

c) Weitere Antibiotica der Erythromycin-Gruppe 2. Die Carbomycin-Gruppe a) Carbomycine, Leucomycine undSpiramycine b) Weitere Antibiotica der Carbomycingruppe III. Polyen-Makrolide 1. Allgemeines : 2. Konstitutionsaufkliirung von Polyen-Makroliden a) DieKonstitutiondesLucensomycins b) Weitere Polyen-Mak);olide mit bekannter Struktur IV. Primycin, Borrelid'in, die Venturicidine und das Chlorothricin a)Primycin b) Borrelidin c) Die Konstitutionsaufkliirung ger Venturicidine d) Chlorothricin ,..' .

V. Makrolide aus Pilzen 1. Zearalenon 2. Weitere Makrolide aus Pilzen VI. Die Zuckerbausteine der Makrolide 1. Die Aminozucker der Erythromycin- und Carbomycin-Gruppe. ...

a) DieStrukturderMycaminose b) Weitere Aminozucker aus antibakteriellen Makrolid-Glykosiden

2. Mycosamin und Perosamin 3. Lankavose (Chalcose) 4. Die verzweigten Zucker aus Makroliden. , ..

5. WeitereZuckerausMakroliden VII. SchluBbemerkungen Literaturverzeichnis.

Chemie und Biologie der Saponine. Yon R. TSCHESCHE und G. WULFF, Organisch-

Chemischeslnstitut,UniversitatBonn,BRD.461

462

464

464464464467

46946947047047347~

I.Einleitung II. Die Reindarstellung und Strukturermittlung der Saponine

1. Iso1ierung und Reindarste11ung a) A11gemeines b) Die Gewinnung des Rohsaponins c) Auftrennung von Saponingemischen: 2. Strukturermittlung a) A11gemeines b) Vo11stiindigeHydro1yse (X) Ag1ykone 1:1) Zucker y) Siiuren ,

VIII lnhaltsverzeichni!; Content.

473

475

477

478

478

479

479

492

493

49341)4

500501

502

503

503

506

524

527

532

534

539

549

552

552

558

560

560

562

564

564

565

569

570

571

573

575

576

c) Methylierung d) Partialhydrolysen e) Konfiguration der glykosidischen Bindung III. DieStrukturderneutralenSteroidsaponine 1. AllgemeineBemerkungen 2. TabellenderneutralenSteroidsapogenine 3. Furostanolglykoside 4. Nuatigeninglykoside 5. Spirostanolg1ykoside a) Allgemeines b) Glykoside mit Zuckern am OH an C-3 des Ag1ykons c) Glykoside mit einem Zuckeranteil, der nicht an das OH am C-3 des

Aglykons gebunden ist d) Glykoside mit mehr als einer Zuckerkette am Spirostanol-Aglykon 6. Polypodosaponin-Typ IV. DieStrukturderTriterpensap°!line 1. Allgemeines 2. TabellenderTriterpenaglykone 3. Neutrale,monodesmosidischeGlykoside 4. Estersaponine 5. DurchUronsaure saure Monodesmoside 6. DurchdasAglykonsaureMonodesmoside 7. Neutrale Bisdesmoside 8. MonodesmosidischeAcylglykosen 9. Durch Aglykon und ZuckeranteiI saure Monodesmoside 10. SaureBisdesmoside 11. Tierische Saponine V. Biosynthese der Saponine 1. DieBiogenesederSteroidsapogenine 2. Die Biogenese der pentacyclischen Triterpensapogenine. VI. Eigenschaften der Saponine 1. Allgemeines 2. HamolyseundSaponinbegriff 3. Die antibiotische Wirksamkeit 4. WirksamkeitgegenInsekten 5. Toxizitat der Saponine 6. PharmakologiederSaponine 7. QuantitativeBestimmungderSaponine Literaturverzeichni~ -

Namenverzeichnis. Author Index

~Q~hWOr7o;phn;. ~..h;op.. Indov

607

;;.,.,

Inhaltsverzeichnis. Contents

2

3

3

5

6

9

13

17

20

23

24

35

47

48

50

53

Recent Developments in the Chemistry of Penicillins. By D. N. MCGREGOR, Research

Division, Bristol Laboratories, Division of Bristol-Myers Company, Syracuse,

New York, USA I. Introduction ' II. Nomcnclature III. Reactionsatthef3-LactamRing A. Acylationofthe6-AminoGroup B.Alkylationofthe6-AminoGroup C. Hydrolysisofthe6-AmidoGroup D. Epimerizationatthe6-Position E. Diazotizationofthe6-AminoGroup F. Substitution at the 6-Position G. CleavageoftheC-7-N-4Bond IV. Reactions at the Thiazolidine Ring. A. RearrangementsofPenicillin Sulfoxides B. OtherThiazolidineRingCleavages C. MiscellaneousNuclearTransformations D. Modificationofthe3:.CarboxylicAcid V. Conclusion. References.

63

64

65

68

68

6969

The Antibiotic Complex of the Verrucarins and Roridins. By CH. T AMM, Institut fiir

Organische Chemie, Universitat Basel, Schweiz I. Introduction. II. Productio\l and Isolation. , .

lII. StructureandChemicalTransformations : I. Sterols. 2. Chromane Derivatives. : 2.1. Myrochromanol andMyIochromanone

Inhaltsverzeichnis. ContentsIV

707074

747584888989949596.

99

99

100

102

l02

103

112

112

112

1)3114

114

114

3. Pyrrole Derivatives. 3.I.VerrucarinE 3.2. Verrucarin G 4. Macrocyclic Trichothecane Esters. 4.1. Verrucarol and Roridin C (Trichoderrnol)

4.2. Verrucarin A and 2'-Dehydroverrucarin A

4.3. Verrucarin B 4.4. Verrucarin J 4.5. Roridin A 4.6. Roridin D 4.7. Roridin E 4.8. Roridin H 5. Wortmannin ,

IV. TotalSynthesis V. MethodsofAssay VI. Biosynthesis I. PyrroleDerivatives 2. TrichothecaneEsters vn. BiologicaIActivity I. Antibiotic Activity. 2. CytostaticActivity 3. Toxicity. 4. Structure and Biological Activity. Acknowledgement. References.

119

119

123

124

124

127

128

128

131

132

132

134

134

134

136

137

Aflatoxins and Sterigmatocystins. By JOHN C. ROBERTS, Department of Chemistry, The

University, Nottingham, England. I. Introduction II. Isolation and Characterisation of the Mycotoxins. III. Structural Elucidationofthe Mycotoxins I. Sterigmatocystin 2. Other Metabolites Closely Related to Sterigmatocystin :.

3. Aspertoxin 4. Atlg.toxin-BI,-B2, -GI,and -G2 5. Aflatoxin-MI and -M2 6. Aflatoxin-B2a and -G2a. IV. Synthesis of the (:t)-Forms of the Mycotoxins and of Related Compounds. I. Tetrahydro-4-hydroxy-6-methoxyfuro[2,3-b]benzofuran 2.Tetrahydrodeoxoaflatoxin-BI 3. Aflatoxin-BI ; 4. Aflatoxin-B2 : ;, AAQtny;n_r.1

lnhaltsverzeichnis. Contents v

137

139

139

140

140

144

147

148

6.Aflatoxin-MI 7. Dihydro-O-methylsterigmatocystin

8. O-methylsterigmatocystin V. Biogenesis of the Mycotoxins I. Sterigmatocystin 2. Aflatoxin-BI VI. Conclusion References

153

153

153

155

159

169

173

174

177

191

191

193

194

200

201

203

204

205

206

FlavoDoid-Glykoside. Von H, WAGNER, Institut fiir Pharmazeutische Arzneimittellehre,

UniversitiitMiinchen,BRD """, I. Strukturtypen von Flavonoid-O-Glykosiden und ihre Verbreitung I. Glykosidierungsmuster 2.0-Monoside 3.0-Bioside 4. 0- Trioside, Tri-, Tetra- und Poly-O-Glykoside 5.0-Glykuronide , 6.Acyl-0-Glykoside II. Flavonoid-C-Glykoside , III. SynthesevonFlavonoidglykosiden I.DarstellungvonAcetobromzuckern 2.SynthesevonO-MonosidenundO-Biosiden a) GlykosidierungderC7-OH-Gruppe , b) GlykosidierungderC3-OH-Gruppe : c) Glykosidierung der C4,-C2,-C3,-Cs-OH~Gruppen 3.Synthese von Flavonoid-O-Bisglykosiden 4.SynthesevonFlavonoid-C-Glykosiden ,.., Addenda , Literaturverzeichnis

217

218

219

222

226

227

227

?~O

.Biogenetic- Type Syntheses of Polyketide Metabolites. By TH. M. HARRJS, C. M. HARRIs,

and K. B. H[NDLEY, Department of Chemistry, Vanderbilt University, Nashville,

Tennessee,.USA I. Introduction. : : {I. Early Studies. , ;. III. Modem Concepts of Polyketide Biosynthesis. :, ...

IV. Experimental Support for the Polyketide Theory ,: :; :...

V. Synthesesof~PolycarbonyICompounds :.:; I. 3,5-DiketoAcidsandEsters , 2. 1.3.5-Triketones

Tnha.1t.ver7eichni. Content.VI

231

234

236

237

238

239

239

240

241

241

243

244

246

246

246

247

259

261

263

263

264

265

265

265

269

274

')'7A

3. 3,5,7- Triketo Acids and Esters. 4.1,3,5,7-Tetraketones 5. 3,5,7,9-Tetraketo Acids and Esters. 6. 1,3,5,7,9-Pentaketones 7. 3,5,7,9,11-Pentaketo Acids and Esters. 8.1,3,5,7,9,11-Hexaketones 9. J3-Heptacarbonyl Compounds. 10. J3-0ctacarbonyl Compounds. 11. J3-Nonacarbonyl Compounds. 12. Reduced Polycarbonyl Compounds. VI. Cyclizations of J3-Folycarbonyl Compounds. 1. Using Several Ketide Fragments. 2. Using a Single Polycarbonyl Compound. a) With3,5-DiketoAcids b) With 1,3,5-Triketones c) With 3,5,7-Triketo Acids and Esters. d) With 1,3,5,7-Tetraketones e) With 3,5,7,9-Tetraketo Acids and Esters. f) With 1,3,5,7,9-Pentaketones g) With J3-Hexacarbonyl Compounds. h) With J3-Heptacarbonyl Compounds. i) With J3-0ctacarbonyl Compounds. j) With J3-Nonacarbonyl Compounds. k) With Reduced J3-Polycarbonyl Compounds. ...

3. Using Partially Cyclized Polycarbonyl Compounds

VII. Conclusions References.

283

283

285

285

292

296

298

309

309309314

12&

The Chemistry of Spiro(4.5]DecaDe SesquiterpeDes. By J. A. MARSHALL, Department of

Chemistry, Northwestern University, Evanston, Illinois, USA, ST. F. BRADY,

Merck Sharp and Dohme Research Laboratories, Rahway, New Jersey, USA,

and N. H. ANDERSEN, Department of Chemistry, University of Washington,

Seattle, Washington, .USA A. Introduction B. TheAcoranesandAlaskanes I. Structure Elucidation of the AcQrus Spiranes ; 2. TheAlaskanes,PrecursorsofCedrene 3. Mass Spectral Considerations. ; 4. Synthesis C. The Spirovetivanes I. Structure , a) Agarospirol , br 13-Vetivone and Related Compounds :

2. Synthesis

VIIInhaltsverzeichnis. Contents

342

342

346

351

353

364

371

D.BiogeneticConsiderations I. The Relationship between Spirovetivanes and Hydronaphthalenic Sesqui.

terpenes ,

2. Alaskane-Acorane Spiranes as Precursors of Tricyclic Sesquiterpenes 3. Chemical Simulation of Biogenetic Pathways involving Spiro[4.5] Decanes ..

E. Tables of Naturally Occurring Spiro[4.5]Decanes Addend um References.

377

378

381

381

381383

385

386

386

392

398

398

401

404

405

410

410410410411411414416417419419420421

422

422427

Phorbolesters -the Irritants and Cocarcinogens or Croton Tiglium L. By E. HEcKER and

R. SCHMIDT, Biochemisches Instilut, Deutsches Krebsforschungszentrum, Heidel-

berg,BRD I. Introduction 2. FractionationofCrotonOil 2.1. General Analytical Chemical Procedures and Biological Assays. 2.1.1. Methods of Separation and Criteria of Purity. 2.1.2. MonitoringofFractionationSteps 2.2. Pr~paration of the Hydrophilic and the Hydrophobic Portions. 2.3. Phorbol Diesters from the Hydrophilic Portion. 2.3.1. Isolation and Resolution of Croton Oil Factor Groups A and B ...

2.3.2. Chemical Characterization of the Croton Oil Factors from Groups A

andBasDiestersofPhorbol 2.4. Higher Phorbol Esters from the Hydrophobic Portion. 2.4.1. Isolation und Resolution of Croton Oil Factor Groups A' and B' 2.4.2. Separation and Chemical Characterization of the Croton Oil Factors

fromGroupsA'andB' 3. Chemistry of Phorbol and of the Croton Oil Factors. 3.1. StructureandStereochemistryofPhorbol 3.2. Reactions Altering the Functional Groups of Phorbol 3.2.1. Functional Derivatives of the Carbonyl Group. Reaction with (::arbonyl Reagents Reduction ofthe Carbonyl Group , 3.2.2. Functional Derivatives of the Hydroxyl Groups. Phorbol Esters. Phorbol Ethers. Oxidation ofSingle Hydroxyl Groups Substitution and Elimination of Hydroxyl Groups. 3.2.3. Functional Derivatives Involving the C=C-Bonds Catalytic Hydrogenation. ..: BrominationandHydrobromination Oxidation. :. 3.3. Structure ofthe Croton Oil Factors , 3.3.1. Phorbol Diesters from the Hydrophilic Portion. : J3.2. Phorbol Triesters from the Hydrophobic Portion.

VIII lnhaltsverzeichnis. Contents

428

428428428429431

436

436438

¥o443

444

447

450

451

454

455

457

458

3.4. Reactions Altering the Tigliane Skeleton of Phorbol and of Neophorbol 3.4.1. Dehydrogenation of Phorbol and 3-Deoxo-3f3-hydroxyphorbol 3.4.2. Oxidative Ring Opening of Phorbol and Derivatives. Ring A Ring B Rings C and D (Bicyclo[4.1.0]heptane System) 3.4.3. Rearrangements in Phorbol and Neophorbol involving the Bicyclo[4.1.0]-

heptaneSystem Crotophorbolone-enol-13,20-diacetate and Acetoxycrotophorbolone-

20-acetate Phorbobutanone and Phorboisobutanone The ..Flaschentriiger Reaction" l2,13-Ketol Rearrangement in Neophorbol 4. Further Diterpenes and Diterpene Esters from Croton Oil. 4.1. Chemistry of 4(X-Phorbol 4.2. Chemistry of 4-Deoxy-4(X-phorbol and 4-Deoxyphorbol 4.3. Compound Groups D, E, D' and E' from Croton Oil. 4.4. Composition of Croton Oil with Regard to Diterpenes and their Esters. ...

5. On the Biological Activities of the Isolated Diterpenes and their Esters. 6. Conclusions and Perspectives. References

Stereoselektiye Totalsynthese yon lndolalkaloiden. Yon E. WINTERFELDT. lnstitut fUrOrganische Chemie der Technischen Universitat Hannover. BRD 469

Literaturverzeichnis ~IR

Structure, Chemistry, and Biosynthesis ofthe Melanins. By G. A. SWAN, Department of

Organic Chemistry, The University ofNewcastle upon Tyne, England. 521

I. Introduction 522

II. EnzymicNatureofMelanogenesis 524

I. Melanogenesis in Invertebrates and Plants. 524

2. Melanogenesis in Vertebrates. 528

3. The Enzyme. 530

III. Allomelanins 532

I. Catechol-Melanin 532

2. NaturalAllomelanins 537

IV. Eumelanins 540

I. Chemical Investigations on Dopa-Melanin and 5,6-Dihydroxyindole-Melanin 540

I.I. Introduction. 540

1.2. StudiesonModelCompounds 540

1.3. IsotopicandDegradativeStudies ~ 542

1.4. Conclusion Regarding the Structure of Melanin. 551

1.5. Studies Relevant to the Structure of the Melanoproteins 553

IXInhaltsv~rzeichnis. Contents

554554554558561561561

562562562563

565

567

570

574

575

582

2. Chemical and Biochemical Investigations on Naturall;:umelanins 2.1. Introduction 2.2. Sepiomelanin ;, 2.3. MelaninfromMelanoma : 2.4. MelaninfromHair 2.5. MelaninfromtheEye 2.6. Other Melanins. 3. Investigations on Melanins by Spectroscopic and other Physical Methods

3.1. UltravioletandInfraredSpectra 3.2. X-RayDiffraction 3.3. ElectronSpinResonance 4: Adrenochrome-Melanin 5. Dopamine-Melanin V. Phaeomelanins VI. Conclusions. References. :-. Addendum

Mechanisms of Corrin Dependent Enzymatic Reactions. By G. N. SCHRAUZER, Department of Chemistry. University of California. San Diego. La Jolla. California. USA

583

584

584584587589

592592598600603609

610610614616617618

I. Introduction. " " ..." ..."

II. Nomenclature. " " ..." III. Properties and Reactions of Corrins and Related Compounds

I" Vitamin BI2 Chemistry. " 2. Vitamin BI2 Model Compounds .."" 3. Coenzyme BI2 Reactions " " IV. Coenzyme BI2 Dependent Enz:ymatic Reactions. ..." " .." " " ."

I. Dioldehydrases " .." " " ..."

2" Ethanolamine Deaminase " "".."""..

3. Ribonucleotide Reductase. .." " " ..." " ..." " .." " " ..

4. M utases " " " .." ." 5. Aminomutases...: ""..."" ".."""..""

V. Corrin Dependent Enz:ymatic Reactions. " " .." .." " " ..." .

I. MethaneBiosynthesis ""."".."" " 2. Acetate Biosynthesis " ""."""."".""..."""...""

3. Methylarsine Biosynthesis. " " " ." " ..." " ..." .

4.Methylmercury Formation.""." ".."".."".""".." 5. Methionine Biosynthesis. .." " " " " ." " " " ..." ..

References.


Sachverzeichnis. Subject Index

629

649


List of Contributors. Mitarbeiterverzeichnis VIII

Carboxylic Acids in Petroleum and Sediments. By W. K. SEIFERT

2

.2

3

4

6

6

II

12

12

15

17

17

19

22

24

31

33

33

36

38

39

39

40

41

42

44

I. General. I. Introduction 2. Occurrence 3. Derivatization II. ParaffinicAcids I. LinearFattyAcids 2. UnsaturatedFattyAcids 3. Iso and Anteiso Acids. 4. IsoprenoidAcids 5. ..Pseudo" Isoprenoid Acids. III. CyclicSaturatedAcids I. MonocyclicAcids 2. Bi- and Polycyclic Naphthenic Acids. 3. TricyclicTerpenoidAcids 4. SteroidAcids : 5. PentacyclicTriterpenoidAcids IV. Aromatic Acids. I. Mono-andDiaromaticAcids 2. Polynuclear Aromatic and Heterocyclic Carboxylic Acids

V. The Origin of Petroleum Carboxylic Acids. VI. BifunctionaIAcids I. DicarboxylicAcids 2. Hydroxy- and Ketoacids 3. Amino Acids. 4. Miscellaneous References.

TV Inhaltsverzeichnis. Contents

Naturally Occurring 2,5-Dioxopiperazines and Related Compounds. By P. G. SAMMES' 51

51

54

58

60

69

80

87

106

107

I. Introduction. II. Synthesis of 2,5-Dioxopiperazines III. Conformations of Dioxopiperazines ...

IV. Simple Dioxopiperazines V. The Echinulins and Related Derivatives

VI. Hydroxypyrazine Derivatives. VII. Sulphur-bridged Dioxopiperazines. VIII. Bicyclomycin and Dibromophakellin ..

References

Structural Investigations of Natura! Products by Newer Methods of NMR Spectroscopy.By R.J. HIGHET and E.A.SOKOLOSKI 119

120

120

121

i22

124

126

130

131

132

135

135

139

141

141

144

144

149

150

150

152

154

157

162

162

I. Introduction. II.SolventEffects III. Derivatives and ]n Situ Reactions. IV.CouplingConstants V. Superconducting Magnets. VI. Lanthanide Induced Shifts. VII. Computer-Aided Interpretation of Spectra

VIII. INDOR IX. The Nuclear Overhauser Effect. X. Fourier Transform Techniques. I. Instrumentation. 2. Proton Spectra from Small Samples. ...

XI.13CSatellites XII.OtherNuclei XIII.13CNMRSpectra I.GeneralDiscussion 2. Sample Size and Acquisition Times. ...

3. Chemical Shifts of Alkyl Residues. 4. Functional Group Recognition. 5. Substituent and Stereochemical Effects .

6. Biogenetic Studies. 7~ Relaxation Studies. XIV. Complementary Studies. References


Applications of the Chiroptical Techniques to the Study of Natural Products. By P. M.

SCOPES 167

I.Introduction 168

1. Units and Definitions. 169

2. Logic of Applications. : 171

II. Allocation of Configuration. 172

1. Carbonyl Chromophores in Steroids and Terpenes: Empirical Correlations. ..172

a)Hexahydroindan-l-and2-ones , 172

b) Bicyclo-[5,3,0]-octanones 174

c) Decalones 175

.d) 4,4-Dimethyl-3.:oxo-Steroids and Triterpenes 178

e) OrientationoftheSteroidalSideChain 180

t) MonocyclicandAcyclicKetones 182g) Difference Curves in Dicarbonyl Compounds. 183

h) Epoxyketones 185

2. Carbonyl Chromophores: Application ofthe Octant Rule. 186

a) trans-Decalones 186

b) cis-Decalones 190

c) FlexibleMonocyclic,Cyclohexanones 192

d) Cyclopentanones 193

e) CycloheptanonesandCyclobutanones 196

t)Epoxy-andCyclopropyl Ketones 1.96

3. Unsaturated Ketones. 197

a) Empirical Correlations. 198

b) HelicityRule 201

4. Dienes and Polyenes 202

a) He1icityRulesforDienes 202

b) CarotenoidsandRelatedCompounds ~ 202

5.AromaticChromophores 204

a) TetrahydroisoquinolineAlkaloids 205b) Indole Alkaloids. 208

c) Oxindole and Isoindole Alkaloids. 211

d) AryltetralinsIncludingLignans 212

e) Aryltetrahydroisoquinolines 214t) Flavans: Isofiavans and Related Compounds. 214

g) OtherAromaticCorrelations , 217

h) Biphenyls. 219

i) Purilie and pyrimidine Chromophores in Nucleosides 219

6.TheCarboxylChromophore 221

a) Correlations Involving Acids or Modified Groups as Principal Chromophore 221

b) Correlations Involving Degradation to a Carboxylic Acid Fragment. 224

c) Empirical Correlations in Complex Lactones and Lactams 226

d) Saturated Lactones: Correlations by Semi-Empirical Ru1es : ..228

e) cx,[3-Unsaturated Lactones 230

7.ChromophoricDerivatives 232

III.StudiesofConformation 235

IV.PositionofFunctiona1Groups 240

Inhaltsverzeichnis. ContentsVI

243

245

247

248

249

V. Detection of Optical Activity. ..

VI. Identity of Two Samples. VII. Reaction Kinetics and Equilibria

Acknowledgement. References.

267

267

268

269

269

270

271

276

280

281

286

288

288

288

289

290

291

Chemistry and Biosynthesis of Plant Galactolipids. By H. C. VAN HuMMEL

I. Introduction. Il. Occurrence and Localization. IIl. Structure Determination and Synthesis. 1. Fractionation : 2. Identification and Structure Determination. 3. Synthesis of Galactosyl Glycerol and Galactosyl Diglycerides 4. Semi-Synthesis 5. Fatty Acid Content. IV. Biosynthesis V. Enzymatic Hydrolysis. VI. Function. 1. Galactolipids in Chloroplast Membrane Structure. 2. Galactolipids and the Synthesis of Fatty Acids. 3. Galactolipids and Electron Transport 4. OtherFunctions References.

Recent Advances in Polynucleotide Synthesis. By H. KOSSEL and H. SELIGER 297

298

299

300

300

304

305346

348

352

353

353

354

355

Introduction. Abbreviations and Sym~ols I. Protecting Groups. 1.1. GeneraIConsiderations 1.2. Choice of Blocking and Deblocking Conditions. 1.3. Survey of Blocking Groups. 1.3.1. Protecting Groups for the Phosphate Moiety. 1.3.2. Protecting Groups for the Hydroxyl and Amino Functions of the Sugar

andBaseMoieties 1.3.3. Protecting Groups for the Vicinal Diol Group of Ribonucleic Acid ton-

stituents , 1.4. Protecting Groups with Special Applications. 1.4.1. Protecting Groups for Solvent Extraction. 1.4.2. Protecting Groups for Separations by Affinity Chromatography. 1 41 A"tiv"hl" Prntectin" Grnlln!!

lnhaltsverzeichnis. Contents VII

356

357

367

368

393

394395396397

397

401

401401404

405

406

406

406406419429

430430431434455456

457457459460461

463

464

471

478

483

1.5. Strategy of Consecutive Blocking or Deblocking of Several Functions. .

1.6. General Blocking Schemes for Intermediates of Polynucleotide Synthesis

2. Phosphorylation Methods in the Synthesis of Mono- and Oligonucleotides. .

2.1. TransferofaPhosphorylGroup 2.2. TransferofaPhosphateGroup 2.3. Miscellaneous Chemical Phosphorylation Reactions. 2.3.1. Phosphorylation by Oxidation of Nucleoside Phosphites 2.3.2. "Thermal'.Phosphorylation 2.3.3. Prebiotic Phosphorylations 2.4. Enzymic Phosphorylation. 3. SeparationTechniques. 3.1. ColumnProcedures 3.1.1. Column Chromatography on Conventional Adsorbent Types. ...

3.1.2. Column Chromatography on Newly Developed Adsorbent Types .

3.2. ExtractionProcedures : 3.3. Miscellaneous Techniques. 4. Formation of Internucleotide Linkages by Chemical Synthesis. 4.1. ConventionalMethods 4.1.1. SynthesisintheDeoxySeries 4.1.2. SynthesisintheRiboSeries 4.1.3. Modified Oligonucleotides. 4.2. Polymer-Support Synthesis of Oligonucleotides. 4.2.1. GeneralReactionPrinciple 4.2.2. Requirements for Supports and Reactants. 4.2.3. Chemical Synthesis of Oligonucleotides on Supports. 4.2.4. Enzymatic Synthesis of Oligo- and Polynucleotides on Supports .

4.2.5. Miscellaneous Uses of Supports in Nucleotide Chemistry. 4.3. Miscellaneous Methods in Chemical Oligonucleotide Synthesis. 4.3.1. Chemical Synthesisvia Activation of Hydroxyl Functions. 4.3.2. Chemical Synthesis via Preactivated Phosphate Derivatives. 4.3.3. Chemical Synthesis Using Unprotected Nucleotides 4.3.4. Chemical Synthesis on Complementary Templates. 5. Formation of Internucleotide Linkages by Enzymic Reactions. 5.1. Reactions Catalyzed .by Polymerizing Enzymes. 5.2. Reactions Catalyzed by Polynucleotide Ligases 5.3. SyntheticReactions Catalyzed by Ribonucleases References


Sachverzeichnis. Subject Index .

509

532


VIIIList of Contributors. Mitarbeiterverzeichnis

11

12

21

22

28

33

41

42

46

51

51

55

58

59

64

Natural Products from Porifera. By L. MINALE, G. CIMINO, S. DE STEFANO,and G. SODANO

I. Introduction. II. Structure Determination and Chemistry 1. Bromo-Compounds , ...

1.1 Tyrosine-Derived Bromo-Compounds 1.2 Miscellaneous Bromo-Compounds 2. Terpenes 2.1 Sesquiterpenes 2.2 Diterpenes 2.3 The C21 Furanoterpenes 2.4 Sesterterpenes 3. Compounds of Mixed Biogenesis: Mevalonate-Benzenoid Precursor. 4. Sterols 4.1 ..Conventional"Sterols 4.2 '.Unusual" Sterols 4.3 Sterol Biosynthesis in Sponges. 5. Miscellaneous Compounds. III. Distribution IY. Pharmacological Properties. Addendum. References.

73

74

83

83

88

Biogenetic-Type Rearrangements of Terpenes. By R. M. CoATES A.Introduction B. Monoterpenes. :

1. Chrysanthemanes, Lavandulanes, Artemisanes, and Santolinanes

2. Menthanes. Pinanes. Camphanes, Fenchanes, and Thujanes


96

101

110

113

130

138

142

145

149

151

156

156

161

164

168

172

172

178

183

181

194

202

205

C. Sesquiterpenes I. Bisabolanes, Sesquicamphahes, Santalanes, and Carotanes 2. Germacranes, Eudesmanes, Guaianes, Cadinanes, and Cubebanes 3. Humulanes, Caryophyllanes, andHimachalanes 4. l,n-Hydrogen Eliminations and l,n-Hydrogen Rearrangements. 5. Eremophilanes, Vetispiranes, Valeranes, and Cyperanes 6. Cuparanes, Chamigranes, Thujopsanes, and Widdranes 7. Patchoulanes and Seychellanes. 8. Copaanes, Copabornanes, Ylanganes, and Sativanes 9. Longipinanes, Longibornanes, and Longifolanes 10. Acoranes, Cedra\les, and Zizaanes D. Diterpenes : I. Labdanes, Clerodanes, Pimaranes, and Rosanes 2. Abietanes, Strobane, and Cleistanthane 3. Beyeranes, Kauranes, Atis~nes, and Trachylobanes 4. Gibberellanes,Grayanes,andAconanes E. Triterpenes I. Squalene. 2. Lanostanes, Cycloartanes, Euphanes, and Tirucallanes 3. Melianes, Cucurbitacins, and 9(10-..19)"4beo-pregnanes 4. Lupanes, Germanicanes, Taraxastanes, Oleananes, and Ursanes 5. Taraxeranes, Multiflorane, Glutinanes, Friedelanes, Isoursane, Phyllanthane.

Bauerane, and Shionanes. 6. Hopanes,Fernanes,Adinanes,andFilicanes Re fere nce s

231

232

234

234

237

239

240

241

241

242

242

244

245

245"c.

Chemistry of the Ansamycin Antibiotics. By K. L. RINEHART, JR., and L. S. SHIELD

I. Introduction. II. Structures ofthe Naturally Occurring Ansamycins A. Streptovaricins B. Rifamycins C. Halomicins D. Tolypomycins E. Naphthomycin F. Geldanamycin G..Maytansinoids : H. Three-dimensionalStructures :.

III. Rea~tionsoftheAnsamycins A. Streptovaricins I. Degradations.') n~~;uot;7ot;nno


256256263

270

271271274

274

275275275

278

280

281

281

283

288

289

291

297

298

300

B.. Rifamycins 1. Degradations. 2. Derivatizations C. Halomicins D. Tolypomycin I. Degradations. 2. Derivatizations E. Naphthomycin F. Geldanamycin I.Degradations 2. Derivatizations G. Maytansinoids .I H. Conclusions Regarding Bioactivity. ...

IV. Physical Properties of the Ansamycins ..

A. Ultraviolet, Rotatory, Infrared Spectra

B. Magnetic Resonance Spectra. C. Mass Spectra. V. Biosynthesis of the Ansamycins A. Streptovaricins B. Rifamycins .C. Geldanamycin References.

The Chemistry of Tryptophan in Peptides and Proteins. By A. FONTANA and C. TONIOLO 309

Acknowledgements 311

I. Introduction 311

11. General 312

I. StructureandReactivity 312

2. ChemicalSynthesis 314

3. Biosynthesis. 318

4. Aspects of Metabolism. 320

III. Chemistry of the Modification and Cleavage of the Tryptophanyl Peptide Bond 323

I. Chemical Oxidation. 324

1.1. Peracids 324

1.2. Ozone 328

1.3. Miscellaneous Oxidations. 329

2. Photooxidation , 331

2.1. Irradiationby.Ultraviole(Light 331

2.2. Dye-SensitizedPhotooxidation :..333

2.2.1. Conversion of Tryptophan to Hexahydropyrroloindole , .335

2.2.2. Conversion of Tryptophan to Quinazolines 331

2.2.3. Conversion of Tryptophan to Carbolines : 338

')~ Tnn;7;naR"tii"tinn 339

T nhaltsverzeichnis. Contents

340340346348

349349353

356356358

363

365

367

368

369

369

371

371

372

172

3. Brominating Agents. 3.1. N-Bromosuccinimide 3.2. BNPS-skatole 3.3. Tribromocresol. 4. 2-Hydroxy-5-nitrobenzyl Bromide (Koshland's Reagent)

4.1. ChemistryoftheReaction 4.2. Other Nitrobenzyl Reagents. 5. SulfenylHalides 5.1. General 5.2. Chemistry of the 2- Thioether-indole Function. 6. Isotopic Labelling. 7. C-Acylation 8. N-Formylation 9. Cyclodehydration 10. Reaction with_Nitrite 11. Reaction with Tetra1litromethane 12. ReactionwithDiazoniumSalts 13. Reaction with 3-Acetoxyxanthine 14. Reaction with Trichloroisocyanuric Acid. 1~ Mi"ce11aneou"

J74

375

378

378

381

381

383

383

384

384

386

IV. Analytical Determination. I. AcidHydrolysis 2. BasicHydrolysis 3. Spectrophotometry. 4. Colorimetry 4.1. p-Dimethylaminobenzaldehyde

4.2. SulfenyIHalides 4.3. Koshland's Reagent. 5. OtherMethods 5.1. N-Bromosuccinimide. ~2 Mi.ceI1aneo\l.

387

387

389390393

396396398399

400400402

4m

v. StructureDetermination 1. Ultraviolet Absorption. 2. CircularDichroism 2.1. Magnetic Circular Dichroism. 2.2. Circular Polarization of Luminescence. 3. NuclearMagneticResonance 3.l.1H-NMR 3.2. 13C-NMR 3.3. 14N-NMR : 4. X-Ray and Conformational Energy Calculation Studies

4.1. X-Ray Structure Determination. ; 4.2. Conformational Energy Calculations. 5. ChargeTransfer.Interactions

"

VIIInhaltsverzeich,,;~. Contents

405

405

407407409410414

416

422

422

424

424

426

VI. SynthesisofTryptophanPeptides I. Synthesis in Solution and in the Solid Phase. 2. SpecialCases ..., 2.1. Glucagon. c 2.2. Valine-gramicidin A 2.3. Luteinizing Hormone-Releasing Hormone. 2.4. ToxinsofAmanitaPhalloides VII. The Role of Tryptophan in the Biological Function of Enzymes

I. Lysozyme. 2. Dehydrogenases VIII. Conclusion. Note Added in Proof. References

451

451

456

460

466

467

471

478

481

488

506

514

516

517

~17

The Present Status of Flavin and FI:;vocoenzyme Chemistry. By P. HEMMERICH

I. Introduction: History and Outlook II.Nomenclature III. Mechanism of Flavin-Dependent Oxido-Reduction IV. Flavoquinone V. Flavin Radicals. VI. Dihydrofiavins VII. Flavin-Substrate Complexes , VIII. Flavin-Acceptor-Complexes IX. New Flavocoenzymes X. Flavin Photochemistry. XI. Flavin-Dependent Photobiology XII. Concluding Remarks Note Added in Proof. References. :


Sachverzeichnis. Subject Index . 553

Inhalt~verzeichnis. Contents

Mitarbeiterverzeichnis. List of Contributors x

Isonrenoids and Alkaloids of Tobacco. By C. R. FNZELL, W AHLD""n "nrl A J AASEN

2

8

8

I/)

12

12

1.4

15

20

20

21

22

22

24

24

28

35

41

42

44

44

44

48

50

51

55

56

I. Introduction; II. Carotenoids and Acyclic Isoprenoids I. Carotenoids 2.AcyclicIsoprenoids 3.Meroterpenoids 4. Nor-Compounds Derived from Cyclic Carotenoids .

a) General Considerations. b)C1, Constituent C)C13 Constituents d)C12 Constituent e) C11 Constituents. f)C1oConstituents g)CgConstituents 5. Nor-Compounds Derived from Acyclic Isoprenoids

III.Diterpenoids I.Thunberganoids 2. Nor-Thunberganoids. 3. Labdanoids and Nor-Labdanoids IV. Triterpenoids and Steroids V. Cyclic Sesqui- and Monoterpenoids. VI.pyridineDerivatives I. Nicotine. , a) Structure and Synthesis b) Biosynthesis. c) Metabolism in the Growing Plant. d) Post-Harvest Reactions e)Bacterial Degradation , An"h".;n" "nd St.ructurll11v R"I"tpd Cnmnnund~ ..


62

62

64

65

66

3.0thers VII. Pyrrole and Pyrrolidine Derivatives. VIII. pyrazine Derivatives ,

IX. Miscellaneous Nitrogen-Containing Constituents

References

81

82

83

84

86

88

101

113

114

117

118

122

124

126

132

136

137

142

144

144

148

149

156

156

157

160

161

164

168

169

172

172

17,

The Chemistiy of the Eremophilane and Related Sesquiterpenes. By A. R. PINDER

I. Introduction II. BicyclicEremo:philanes I.. Hydrocarbons. 2. Alcohols. 3. Ketones 4. KetoAIcohols 5. Acids. 6. Esters III. Furanoeremophilanes 1. Butenolactones 2. Furanoeremophilanes a) Monohydric Alcohols and Their Ethers and Esters. b) Monoketones c) Epoxides d) Di- and Trihydric Alcohols and Their Esters and Ethers. e) KetoAlcoholsandKetoEsters f) Miscellaneous Furanoeremophilanes g) Furanoeremophi1anes from South African Plants. IV. 4-epj-Eremophilanes V. Bicyclic 7-epj-Eremophilanes (Nootkatanes) 1. Hydrocarbons 2. Alcohols. 3. Ketones 4. Esters. : VI. Tricyclic7-epj-Eremophi1anes 1. Hydrocarbons. 2. Alcohols. 3. Ketones VII. Ishwaranes VIII. B-Noreremophilanes 0 1. TheBakkenolides 2. Other Noreremophilanes IX. Biogenetic Considerations. References

Inhaltsverzeichnis. Contents 'T

187

188

188

190

191

191191192193

193193195195196

198199201203

215215216217217219220222223'

224224226226

226

228

Phytoalexine und verwandte Pt1anzenstoffe. Von D. GROSS I. Einfiihrung II. PriiinfektionelleAbwehrstoffe III. Postinfektionelle Abwehrstoffe. IV. Phytoalexine und phytoalexiniihnliche Verbindungen I. Polyacetylene a) SafinolundDehydrosafinol b) Wyeron c) Wyeronsiiure 2. Dihydrophenanthrene a) Orchinol. .: b) Hircinol c) Loroglossol d) Strukturverwandte Pflanzeninhaltsstoffe 3. Isoflavonoide a) Isoflavane b) Isoflavanone c) Pterocarpane 4. Sesquiterpene a)Rishitin b) Rishitinol c) Glutinoson d) Capsidiol e) Lubimin, 4-Hydroxylubimin und Isolubimin t) Strukturverwandte Sesquiterpene g) Gossypol h) Hemigossypol und strukturverwandte Verbindungen

5. Furanoterpenoide a) Ipomeamaron ..." b) Ipomeamaronol c) Dehydroipomeamaronund 4-Hyaroxymyoporon ...

6. Verschiedenes V. SchluBbetrachtung

Literatur 229

249

250

252

253

253

258

260

7(;1

Studies in SecoDdary Metabolism witb Plant Tissue Cultures. By K- H. OYERTON and

D. J. PICKEN I. Introduction II. The Chemical Potential of Plant rissue Cultures. III. BiosynthesisofPolyisoprenoids I. PlantSterolMetabolism 2. Mechanism of Side Chain Ethylation in Stigmasterol Biosynth.esis 3. BiosynthesisofSteroidalSapogenins 4. BiosynthesisofTriterpenoids

Inhaltsverzeichnis. ContentsVI

5. Isomerisation of trans, trans- and cis, trans-Famesol and the Biosynthesis ofy-Bisabolene 263

6. Biosynthesisofent-Kaurene 267

IV. Biosynthesis of Polyketides 268

1. Biosynthesis of Cyclopropane and Cyclopropene Fatty Acids in Higher Plants 268

V. Metabolism of Aromatic Plant Constituents. 269

I. FlavonoidBiosynthesis 269

2. Anthocyanidin Biosynthesis. 271

3. RetrochalconeBiosynthesis 273

4. AnthraquinoneBiosynthesis 274

5. CoumarinBios'ynthesis 275

6. Catabolism of Aromatic Plant Constituents. 2796.1 General 2796.2 FlavonoidCatabolism 2806.3 Degradation of TyrQsine by the Homogentisate Pathway. 282

VI. BiosynthesisofAlkaloids 284

I. General 284

2. Indole Alkaloids. 285

3. Berberine Alkaloids. 286

4. f3-Carboline Alkaloids. 288

5. Furoquinoline Alkaloids. 288

6. Tropane Alkaloids. 291

References 293

300

300

301

302

302

303

303

303

303308309312315

315

315316316317

Carbazole Alkaloids. By D. P. CHAKRABORTY I. Introduction A. Nomenclature and Electronic Characteristics. B. Occurrence. C.Isolation D. Detection of Caibazoles by Chromatographic Methods

II. Methods of Structure Elucidation. A. Physical Methods. I. Ultraviolet Absorption Spectra. 2. IRSpectra 3. NMRSpectra 4. Mass Spectra 5. X-Ray Crystallographic Methods. B. ChemicaIMethods Degradative Reactions. a) ZincDustDistillation b) Decarbonylation and Decarboxylation. c) Demethylation

VIIInhaltsverzeichnis. Contents

317318

319

319319320320321322322

323

327

328

328

328330332334335336337

j38

338339341342343346347349352352

353

353356356358359359361362363363365366

d) Ozonisation. e) Permanganate Oxidation. C. Synthesis of Carbazoles I. Graebe-Ullmann Synthesis. 2. BorscheSynthesis 3. Watermann and Vivian's Method. 4. Nenitzescu Synthesis. 5. Thermal Synthesis of Carbazoles 6. Photocyclisation of Diphenylamine to Carbazole

7. Anodic Oxidation. 1II. Biogenesis of Carbazole Alkaloids. IV. Biochemical Properties of Carbazole Alkaloids. V. Chemistry of Carbazole Alkaloids. A. Members of the C13-Skeleton Group. I. Murrayanine 2. Glycozoline 3. Glycozolidine 4. MukoeicAcid 5. Mukonine 6. 3-Methylcarbazole 7. Mukonidine

B. Members of theC18-Skeleton Group

1. Indizoline 2. Heptaphylline 3. 6-Methoxyheptaphylline 4. Heptazoline. 5. Girinimbine 6. Koenimbine 7. Heptazolidine 8. Murrayacine 9. Koenigine and Koenidine 10. Koenine

Members of the C23-Skeleton Group. ..

I. Mahanimbine 2. dl-Mahanimbine 3. Mahanimbicine and Isomahanimbine

4. Mahanine 5. Mahanimbinine 6. Murrayazoline 7. Murrayazolinine 8. Murrayazolidine 9. Cyclomahanimbine : 10. Bicyclomahanimbine II. Murrayacinine 12. Bicyclomahanimbicine.

~""References

VIII lnhaltsverzeichnis. Contents

373

374

375

377

377

377

378

380

387

-3B.7

387

387

389

391

392

392

396

398

398

401

402

402

406

406

408

409

409

410

410

416

416

418

418

421

421

422

423

426

427

431

Biirzeldriisenlipide. Von J. JACOB.. I. Einleitung II. AnatomieundHistologiederBiirzeldriise III. Biirzeldriisensekrete I. Analytische Methoden a) Isolierung und Reinigung ; ...

b) Gaschroniatographie(GLC) c) Massenspektrometrie(MS) 2. Zusammensetzung der Biirzellipide bei Arten unterschiedlicher Ordnungen

a) Systematik., , b) Einzelne Ordnungen I. Sphenisciformes 2. Procellariiformes 3. Ciconiiformes. , ...

4. Phoenicopteriformes , ..

5. Anseriformes : 6. Falconiformes 7. Galliformes. 8. Gruiformes 9. Charadriiformes 10. Lariformes II. Columbiformes 12. Psittaciformes 13. Cuculiformes 14. Strigiformes 15. Piciformes 16. Passeriformes 16.1. Corvidae 16.2. Sylviidae 16.3. Paridae 16.4. Fringillidae und Emberizidae 16.5. Ploceidae 16.6. Certhiidae und andere IV. Andere Vogellipide 1. Depotfette : 2. Magenole V. Biosynthese VI. Physiologische Funktion VII. Chemotaxonomieund Systematik Li teratur

439

440

443

443

Hypothalamus-Regulationshormone. Von W. VOELTER

I. Einfiihrung II. ThyreotropiMreisetzendes Hormon A. Strukturaufkliirunll

Inhaltsverzeichnis. Contents IX

446

456

483483484492496502

505

505

506

B. Synthesen vom Thyreotropin-freisetzenden Hormon C. Synthesen von TRH-Analoga. Struktur-Aktivitatsbezi~hungen beim Thyreo-

tropin-freisetzenden Hormon '0 D. Spektroskopische Untersuchungen vonTRH und seinen Derivaten Dl. Infrarotspektroskopie , D 2. Massenspektroskopie D3. lH:.NMR-Spektroskopie D4. 13C-NMR-Spektroskopie D 5. Circulardichroismus III. Luteinisierendes/Follikel-stimulierendes Hormon-freisetzendes Hormon A. Strukturaufklarung B. Synthesen vom ll\teinisierenden/Follikel-stimulierenden Hormon-freisetzenden

Hormon C. Synthesen von LH/FSH-RH-Analoga. Struktur-Aktivitatsbeziehungen beim

luteinisierenden/Follikel-stimulierenden Horrnon-freisetzenden Hormon IV. Somatostatin 516

532

~,4Literatur

565Namenverzeicbnis. Author Index

~RQSachverzeichnis. Subject Index


VTTMitarbeiterverzeichnis. List of Contributors

The Use of Carbon-13 Nuclear Magnetic Resonance SpectroscoPY in Natural Products

Chemistry.ByF.W.WEHRLIandT.NISHIDA

2

2

3

6

12

14

16

23

24

24

33

55

81

104

122

128

163

174

181

183

194

195

216

I. Introduction. 2.13CNMRSpectraIAssignments : 2.1.. Single Frequency Decoupling 2.2. Proton-CoupledSpectra : 2.3. Isotopic Substitution. 2.4. Lanthanide Shift Reagents 2.5. Spin-Lattice Relaxation. 3. 13C Spectral Data of Natural Products. ,

3.1. Terpen9idsandSteroids Monoterpenes. Sesquiterpenes Diterpenes Terpenoids Cn (20 < n <30) Steroids Carotenoids and Related Terpenoids 3.2. Alkaloids 3.3. Purines, Pteridines, Flavonoids, apd Related Substances

3.4. Carbohydrates 3.5. Antibiotics. 4. Biosynthetic Studies. 5. ConcludingRemarks Refere n ces Addendum.

VI Inhaltsverzeichnis. ConteY1t.~

231

231

238

243

252

255

258

260

262

"1;'7

The Role of Heteroatomic Substances in the Aroma Compounds of Foodstuffs. By

G. OHLOFF and I. FLAMENT I.Introduction II. Pyranones, Furanones, and Related Aroma Compounds. III. Sulfur Compounds. IV. Thiophenes , .

V.Thiazoles VI.OxazolesandOxazolines VII. Pyrroles ' Vlll.Pyrazines , ; References.

285

286

287

288

289

290

291

291

291

291

305

315

319

320

349

349

350

352

355

356

370

381

Naturally Occurring Cembran~. By A. J. WEINHEIMER, C. W. J. CHANG, and J. A.

MATSON ; I. Introduction A. Nomenclature. B. StructuraIRepresentation C. Configurations. D. ..Cembrane" E. DistributionofCembranes II. Natural Sources. A.Plants ,

I. ResinousPlants 2. Tobacco. ..: 3. Miscellaneous Plants. B. Insects. C. MarineInvertebrates III. Synthesis A. (:t)-Cembrane B. (:t)-Cembrene C. Other Cembranoids IV. BiosynthesisofCembranoids Tables. Addendum : Reference.

Namenverzeichnis. Author Index JR9

Sachverzejchnjs. Subject Index 409

Contents

List of Contributors IX

2

4

4

6

15

15

51

52

55

65

68

87

91

91

95

98

104

104

109

111

112

115

116

118

I.JQ

Insect Pheromones: A Critical Review of Recent Advances in Their Chemistry, Biology,

and Application. By J. M. BRAND, J. CHR. YOUNG, and R. M. SILVERSTEIN ...

I. Introduction. II.StructureElucidation A. Isolation. B. Identification III.Synthesis A. Coleoptera B.Diptera C. Homoptera D.Hymenoptera : E. Isoptera F. Lepidoptera G. Orthoptera IV.Stereobiology A. GeometricIsomers B. Enantiomers --C. Chemorecognition V. Biosynthesis. : A. Exposure of Bark Beetles to Pheromone Precursors B. Hormonal Influence on Pheromone Production. C. PossibleRoleofMixed-FunctionOxidases D. Possible Involvement of Microorganisms in Pheromone Synthesis. E. BiosynthesisoftheBicyclicKetals , F. BoI!WeevilSexAttractant G. M1scenaneousLabeUingStudiesu n;~t~~, Or;~;n Af" 1>j,~~~"

Contents

119

123

123

127

139

141

146

147

148

149

149

157

VI. Chemosystematics and Speciation. VII. Practical Applications: Status and Projections. A. Plea for Sanity and Integrated Pest Management

B. Forest and Shade-Tree Insect Pests. C. Orchard and Vineyard Insect Pests. D. FieldCropsInsectPests E. Stored Products Insect Pests. F. Pests That Directly Afflict Humans or Animals .

G.PheromoneFormulations VIII. Conclusion. Addendum. ~ References

The Structural Polymers of the Primary Cell Walls of Dicots. By M. McNEIL, A. G.

DARviLL,andP.ALBERsHEIM 191


A. WhyStudytheStructureofCellWalls? 192

B. Availability of Homogeneous Cell Wall Preparations. : ..193

C. GoalsofCeIIWallStructuraIResearch , 194

D. Problems Associated With Cell Wall Structural Research. 195

E. Types of Ce.ll Wall Polysaccharides 196

II. Sugar Nomenclature and Abbreviations Used in this Review. 197

A. GlycosylResidues 197

B. Abbreviations 198

C. Absolute Configuration. 198

D. Anomeric Configuration. 198

E. RingSize 198

F. Linkage Analysis. 198

G. Polymer Names. 199

III. Methods Used in the Structural Analysis of Cell Wall Polysaccharides 199

A. Introduction. 199

B. Solubilization and Fractionation of Cell Wall Polysaccharides 200

C. Quantitative Analysis of the Glycosyl Residues of Oligo- or Polysaccharides 201

D. Uronic Acid Quantitation 201

E. Glycosyl-LinkageCompositionAnalysis 203

F. Sequencing the Glycosyl Residue~ jn Polysaccharides 205.

IV. The Pectic Polysaccharides 208

A. Introduction. : 208

B. Rhamnogalacturonan I. , 208

C. Homogalacturonan 210

n Ar"h"n "1"

Contents VII

E. Galactan 214

F. Arabinogalactan. "'. 217

G. Rhamnogalacturonan II. 220."'

H. Aplogalacturonan ". 221

V. The Hemicelluloses 221

A. Xylogluc~n 221

B. Xylan., ,' 227

VI. Non-Cellulosic Glucan 229

VII.Cellulose 230

VIII. Cell Wall Protein. 231

A. Hydroxyproline-Rich Proteins. ; ..231

B. Hydroxyproline-Rich Glycoproteins With Lectin-Like Properties. 234

IX. Interconnections Between the Primary Cell Wall Polymers of Dicots 235

A. Introduction 235

B. The Pectic Polysaccharides are Covalently Interconnected. 235

C. The Hemicelluloses of Primary Ce!l Wa!ls Bond Strongly to Ce!lulose Fibers 237

D. Is the Hydroxyproline-Rich Glycoprotein of the Ce!l Wa!l Connected to theOtherPolymersoftheCe!lWa!l? 238

E. Are the Xyloglucan Chains Covalently Linked to the Pectic Polysaccharides?239

F. The Current Ce!l Wa!l Model. 239

X. The Future of Primary Ce!l Wa!l Research- New Methods. 240

References 243

251

252

253

253

256

260

262

262

262

267267269

271

272

Dehydroamino Acids, (X-Hydroxy-(X-amino Acids and (X-Mercapto-(X-amino Acids. By

u. SCHMIDT, J. HAusLER, ELISABETH OHLER, and H. POISEL I. Introduction and Scope. , ..

II. Occurrence and Biosynthesis of Dehydroamino Acids, Hydroxy Amino Acids,

Mercapto Amino Acids and the Corresponding Dioxopiperazines A. Occurrence. B. Biosynthesis III. Determination of Strtlcture and Configuration of Dehydroamino Acid Deri-

vati ves IV. Synthesis of Dehydroamino Acid Derivatives. A. AcylenaminoAcidDerivatives ,...

I. Via Oxazolinones. 2. By f3-Elimination Reactions. 2.1 f3-Elimination Reactions of f3-Hydroxy-(X-amino Acid Derivatives. ..

2.2 f3-Elimination Reactions. from Cysteine Derivatives. 3. By N-Chlorination/Dehydrochlorination 4. FromN;.HydroxyaminoAcidDerivatives 5. From Carbonyl Compounds and Isocyanoacetic Ester or Isothiocyanato-

aceticEster 272

VIII Content"

6. By Condensation of cx-Keto Acids With Amides orNitriles 273

7. By Chain Lengthening of ~-Halo-cx-acylaminoacrylic Acid Derivatives. ..275

B. UnsaturatedPiperazinediones 275

I. ByCondensationReactions 275

2. ByRingClosureReactions 275

3. By Elimination Reactions. 277

4. B~ Dehydrogenation. 278

C. Arylidene-enaminoAcidCompounds 278

D. cx-EnaminocarboxylicAcidCompounds 279

E. cx-IminocarboxylicAcidDerivatives 281

F. cx-AcyliminocarboxylicAcidDerivatives 281

V. Synthesis of cx-Hydroxy- and cx-Mercapto-cx-amino Acids, cx,cx-Diamino Acids and

the Corresponding Peptides and Piperazinediones 282

A. Via Oxazolinones 284

B. Direct Oxidation of Amino Acid Derivatives and Piperazinediones 285

C. Interconversion of cx-flydroxy- and cx-Mercapto-cx-amino Acids, Hydroxy-

and Mercaptopiperazinediones, Pyruvoylamino Acid Amides and Dehydro-

peptides 286

VI.ReactionsofDehydroaminoAcids 289

A. EnaminocarboxylicAcidDerivatives 289

I. Reactions of the Amino and Carboxy Groups. 289

2. ReactionsoftheDoubleBond 289

2.1 Additions Leading to ~-Substituted Amino Acids. 291

2.2 Additions Leading to cx-Substituted Amino Acids. 293

2.3 Hydrolysis 294

2.4 Intramolecular Additions. 295

2.5 Catalytic Hydrogenation. 296

B. Addition Reactions to cx-Acylimino- and cx-Iminocarboxylic Acid Derivatives 297

Addendum .

References

298

300

Author Index

Subject Index

Ref. 547.7082 ZEC V.38

CONTENTS

List of Contributors VII

The Mitomycin Antibiotics. 1

I. Isolation and Structure 1

II. Transformation Products 7

III. Mechanism of Action 13

IV. Biosynthesis of the Mitomycins 19

V. Synthetic Studies 22

References 41

The Biogenesis and Chemistry of Sesquiterpene Lactones. 47

I. Introduction 48

II. Germacradiene-Derived Sesquiterpene Lactones 50

III. Germacranolides 58

IV. Eudesmanolides and Biogenetic Derivatives 134

V. Guaianolides and Seco-Guaianolides (Xanthanolides) 166

VI. Elemanolides 214

VII. Pseudoguaianolides and Biogenetic Derivatives 223

VIII. Eremophilanolides and Bakkenolides 257

Referrences 321

Index of Major Charts and Tables 388

Author Index 391

Subject Index 408

Ref. 547.7082 ZEC V.39

CONTENTS

List of Contributors XI

Carbohydrate Derivatives in the asymmetric Synthesis of Natural Products. 1

I. Introduction 2

II. Some Background Information 5

III. Some Attributes of Carbohydrate Synthons 7

IV. Syntheses 9

References 56

Recent Advances in the Biology and Chemistry of Vitamin 63

I. Biology and Biochemistry of Vitamin D 64

II. Partial and Total Synthesis 74

III. Photolytic and Thermal Conversions of the Vitamin D Isomers 105

References 111

Stereochemistry of Naturally Occurring Carotenoids. 123

I. General Introduction 124

II. Historical 126

III. Methods and Application 127

IV. Geometrical Isomerism 148

V. Established Chirality 151

VI. Chirality and Biogenetic Relationships 152

References 164

Chemistry and Biochemistry of y-Glutamyl Derivatives from Plants Including Mushrooms

(Basidiomycetes). 173

I. Introduction 175

II. Nomenclature 176

III. Structures and Distribution of y-Glutamyl Derivatives from Plants 177

IV. Chemical, Spectroscopic, and Analytical Properties of y-Glutamyl Derivatives 217

V. Isolation and Structure Determination of Individual Compounds 229

VI. Synthesis 237

VII. Biosynthesis and Transformations of y-Glutamyl Derivatives in Plants 242

VIII. y-Glutamyl Derivatives with Toxic or Other Specific Biological Properties 261

IX. Compounds Structurally Related to y-Glutamyl Derivatives from Plants 263

X. Summary 266

Acknowledgements 266

Addendum 266

References 267

Author Index 287

Subject Index 301

Ref. 547.7082 ZEC V.40

CONTENTS


Chemistry of Synthetic Immunomodulant Muramyl Peptides.

I. From Freund’s Adjuvant to MDP 2

II. Synthesis of N-acetyl-muramyl-L-alanyl-D-isoglutamine (MDP) 4

III. Synthesis of Other N-acetyl-muramyl-dipeptides, Analogues and Derivatives of MDP 9

IV. Synthesis of N-acetyl-muramyl-tri, tetra, and pentapeptides, and of Some Analogs

Bearing a Lipophilic Group at the C-terminal End 18

V. Synthesis of N-acetyl-B-D-glucosaminy-(1-4)-N-acetyl-muramyl-peptides 23

VI. Synthesis of Oligomers and Conjugates of MDP 29

VII. Mass Spectrometry of MDP and Analogues 30

VIII. 13C-NMR Spectrometry of MDP and Derivatives 33

IX. Analysis of MDP 34

Addendum 35

References 38

Appendix: Leading References on Biological Activities of MDP and Derivatives 43

The Chemistry of Longifolene and Its Derivatives. 49

I. Introduction 50

II. Isolation, Occurrence 50

III. Structure 51

IV. Synthesis 52

V. Isolongifolene 57

VI. Reactions of Longifolene 62

VII. Reactions of Isolongifolene 91

VIII. Ultraviolet Absorption of Some Longifolene Derivatives 95

IX. Biosynthesis 96

X. Longifolene in Industry 97

References 98

Homoisoflavanones and Biogenetically Related Compounds. 105

1. Introduction 106

2. Isolation and Identification 107

3. Structure and Nomenclature 113

4. Chemical Transformations and Syntheses 125

5. Biosynthesis 137

6. Biological Activity 143

7. Chemotaxonomy 145

References 149

Naturally Occurring Phenalenones and Related Compounds. 153

I. Introduction 153

II. Phenalenones and Related Metabolites from Fungi 154

III. Phenalenones and Related Metabolites in Higher Plants 168

References 187

Molecular Mechanisms of Enzyme-Catalyzed Dioxygenation. (An Interdisciplinary Review.) 191

I. Introduction 192

II. Some Basic Chemistry of Molecular Oxygen 193

III. Precedents for Metal-Activation of Dioxygen 196

IV. Precedents for Metal Activation of Organic Substrates 205

V. The Double Bond-Cleaving Dioxygenases 207

VI. The Luciferases 222

VII. Peroxidizing Dioxygenases 225

VIII. Miscellaneous Dioxygenases 230

IX. x-Keto Carboxylic Acid Decarboxylating Dioxygenases 239

X. Summary 249

Acknowledgments 251

References 251

Author Index 267

Subject Index 280

Ref. 547.7082 ZEC V.42

CONTENTS

List of Contributors VII

Chemical Constituents of the Hepaticae 1

I. Introduction 2

II. Chemical Costituents 4

III. Biologically Active Substances 186

IV. Chemosystematics of the Hepaticae 191

Index of Major Charts and Tables 268

References 269

Cross-Reactions of Plant Polysaccharides in Antipneumococcal and Other Antisera, an Update 287

References 294

Author Index 297

Subject Index 302

Ref. 547.7082 ZEC V.43

CONTENTS

List of Contributors VIII

Naturally Occurring Isoflavonoids (1855-1981). 1

I. Introduction 3

II. Distribution 6

III. Biological Activity and Uses 14

IV. Introduction to Tables 2,3 and 4 20

Acknowlegements 22

Table 2. Naturally Occurring Isoflavonoid Aglycones 22

A. Isoflavones 22

B. Isoflavoneqkuinone 84

C. Coumaranochromones 85

D. Isoflavanones 85

E. Rotenoids 98

F. Dehydrorotenoids 116

G. Pterocarpans 121

H. Pterocarpanones 156

I. Pterocarpenes 157

J. Pterocarpenequinones 161

K. Isoflavans 161

L. Isoflavanol 176

M. Isoflavanquinones 176

N. Isoflavenes 179

O. Coumestans 181

P. 3-Arylcoumarins 190

Q. x-Methyldeoxybenzoins 194

R. 2-Arylbenzofurans of Leguminous Origin 197

S. 2-Arylbenzofuranquinone 200

Molecular Weight Index 216

Trivial Name Index 218

Source Index 224

References 229

Note added in Proof 266

The Sarpagine-Ajemaline Group of Indole Alkaloids. 267

1. Introduction 268

2. Skeletal Types 270

3. Occudrrence 279

4. Biogenesis 291

Interlude: Enzymic Transformations 300

5. Chemistry 316

6. Syntheses 318

7. Spectroscopy 324

8. Pharmacology 333

References 334

Author Index 347

Subject Index 363

Ref. 547.7082 ZEC V.44

CONTENTS


Pro-Inflammatory, Tumour-Promoting and Anti-Tumour Diterpenes of the Plant Families

Euphorbiaceae and Thymelaeaceae. 1

I. Introduction 2

II. Classifiacation of Structural Types 3

III. Botanical Considerations 4

IV. Biosnthetic Reclationships 6

V. Isolation of Diterpenes 9

VI. The Macrocyclic Diterpenes 13

VII. Tigliane Diterpenes 27

VIII. Ingenane Derivatives 58

IX. Daphnane Derivatives 73

X. Closing Remarks 87

Acknowledgements 89

Refereknces 90

Bitter Principles of Cneoraceae. 101

I. Introduction 102

II. Nomenclature and Classification 104

III. Constitution and Configuration of Cneorins A, B, C and D 106

IV. The Series of Stereoisomeric 124

VII. C-7 Hemiacetals and Methylacetals with (5S, 10R, 17R)-Configuration 133

VIII. C-9 Hemiacetals with (5S, 8S, 10R)-Ronfiguration 136

XI. Cyclic Peroxides 141

X. Bitter Principles with a y-Lactol Ring (C-15 Hemiacetals) 144

XII. Protolimonoids 168

XIII. Comments on Biosnthesis of Cneorins and Tricoccins 173

References 181

Chemical and Biological Aspects of Marine Monoterpenes. 189

I. Introduction 190

II. Structural Variation 193

III. The Role of Halogens in Biogenesis 195

IV. Relationships Between Taxonomy and Occurrence of Structural Types 200

V. Metabolite transfer and Biological Activity 209

VI. Spectroscopic and Chemical Properties 212

VII. Physical and Spectroscopic Tables 223

Acknowlegement 236

References 236

The C-Nucleoside Antibiotics. 243

I. Introduction 243

II. General Aspects of C-Nucleosides 246

III. Showdomycin 250

IV. The Formcins 264

V. Pyrazofurin (Pyrazomycin) 270

VI. Oxazinomycin (Minimycin) 276

VII. The Ezomycins 279

VIII. Biosynthesis of C-Nucleoside Antibiotics 284

References 290

Author Index 301

Subject Index 312

Ref. 547.7082 ZEC V.45

CONTENTS

List of Contributors VIII

The Chemistry of the Limonoids from Meliaceae. 1

I. Introduction 2

II. Classes of Limonoids 5

III. Outlook for future Work 46

IV. Tables 47

References 93

Recent Progress in the Chemistry of Lichen Substances. 103

1. Introduction 104

2. Carbohydrates 105

3. Amion-acid Derivatives 109

4. 4Ylidenetetronic Acids 111

5. Aliphatic Acids and Rkelated Compounds 113

6. Mononuclear Phenolic Compound from Lichens 123

7. Chromones 127

8. Xanthones 128

9. Anthraquinones and Biogenetically Related Compounds 133

10. Depsides 143

11. Depsidones and Related Diphenyl Ethers 167

12. Dibenzofurans and Biogenetically Related Compounds 200

13. Mevalonic Acid Derivatives 207

14. Lichen Chemotaxonomy 215

References 219

Paralytic Shellfish Poisons. 235

I. Introduction 235

II. Occurrence and Isolation 236

III. Structure and Chemistry 239

IV. Synthesis 253

V. Biosynthesis 256

VI. Pharmacology 259

References 261

Author Index 265

Subject Index 273

Contents

List of Contributors VTTT

3

8

11

17

21

38

49

51

51

53

56

75

78

80

89

NaturaUy Occurring I:I-Lactarns. By R. SOUTHGATE and S. ELSON

I. Introduction. II. Nocardicins III.Monobactams IV.Penicillins V. Clavulanic Acid. VI. Olivanic Acids, Thienamycin and Other Carbapenems VII. Cephalosporins and Cephamycins VIII. Pachystermines, Wild-Fire Toxin and Antimetabolites IX.Biosynthesis I. Biosynthesis ofNocardicinA 2. Biosynthesis of the Monobactams .3.BiosynthesisofthePenicillins 4. Biosynthesis ofClavulanicAcid... 5. Biosynthesis of Carbapenem Antibiotics. 6. Biosynthesis of the Cephalosporins , References.

107

108

109

109

110

112

II')

New Techniques for the Mass Spectrometry of Natural Products. By I. HOWE and

M.JARMAN I. Introduction II. Methods of Ionization. II.I. ElectronImpact II.2. ChemicalIonization II.3. DesorptionChemicalIonization TT d P;plti np.nrnt;nn

VI Content:

113

114

115

115

116

116

117

118

119

120

120

121

127

130

133

135

137

138

139

142

144

146

II.5. Secondary Ion Mass Spectrometry and Fast Atom Bombardment Mass

Spectrometry : II.6. PlasmaDesorptionMassSpectrometry II.7. LaserDesorptionMassSpectrometry II.8. GeneralCommentsandFutureProspects lII. OtherT~hniques in Mass Spectrometry. lII.I. High-MassSpectra lII.2. TandemMassSpectrometry lII.3. CoupledChromatography lII.4. Computers lII..5. QuantitativeMeasurements IV. Applications of the Newer Techniques in Mass Spectrometry to Specific Classes

ofNaturaIProduct.: IV. I. PeptidesandProteins IV. 2. Carbohydrates IV. 3. Nucleotides IV. 4. Tetrapyrroles IV. 5. FattyAcids,Alcohols,andEsters IV. 6. Complex Lipids. IV. 7. Eicosanoids IV. 8. Steroids IV. 9. Antibiotics IV.I0. MiscellaneousNaturaIProducts Re ferences

153

154

154

155

167

167

168

175

.189

.189

.190

.193

.193

.194

19R

Chemical Synthesis of the Trichothecenes. By P. G. McDouGAL and N. R. SCHMUFF

..

I. General Introduction. II. OriginandBiologicalActivity III. Structure. IV. Synthesis of the Simple Sesquiterpenoid Trichothecenes I. Introduction ' 2. The Aldol Approach. 3. The Biomimetic Approach. 4. Miscellaneous Approaches. V. Synthesis of the Trichoverroids 1.1ntroduction 2. TotalSyntheses VI. SynthesisoftheMacrocycles I. Introduction. 2. ModeISystems ~ Vprn"",r;n A

Contents VII

202

207

207

210

211

4. VerrucarinJ 5. VerrucarinB 6. Roridin E and Baccharin B5

7. Vertisporin References

221

222

222

223

223

224

225

235

236

..37

.237

.239

.239

.240

.240

.241

.241

.245

.250

.253

.255

.259

Quassinoid Bitter Principles II. By JUDITH POWNSKY

I. Introduction. , ...

II. Quassinoid General Features. III. Structure Determination of Quassinoids I. Cl8-Quassinoids 2. Cl9-Quassinoids 3. C2o-Quassinoids 4. C25-Quassinoids IV. Physical Methods. V. Biological Activity. I. AntileukemicActivity 2. AntiviralActivity 3. AntimalarialActivity 4. Antifeedant and Insecticidal Properties. ...

5. AmebicidalActivity 6. Anti-inflammatory Activity. VI. ChemicalModifications VII. Synthetic Studies. VIII. Tota1 Synthesis of dl-Quassin IX. Total Synthesis of dl-Castelanolide .X. Tables3-6 Reference"

..

Author Index 265

"..h;~. TndAv ')R(\

Contents


Tremorgenic Mycotoxins. By P. S. STEYN and R. VLEGGAAR I

I. Introduction. 3

2. The Penitrems. Janthitrems, Lolitrems, Af1atrem, Paxilline, Paspaline,

Paspalicine, Paspalinine, and PaspaIitrems A and B ; ...4

2.1 ThePenitrems..: 4

2.1.1 ProducingOrganisms 4

2.1.2 Isolation and Chromatography of the Penitrems. 6

2.1.3 StructureofthePenitrems 8

2.1.3.1 General Aspects, Ultraviolet and Infrared Spectroscopy. 8

2.1.3.2 Nuclear Magnetic Resonance Spectroscopy. 8

2.1.3.3 Mass;pectrometry 17

2.1.3.4 Stereochemistry of the Penitrems: Conformation and Absolute

Configuration 18

2.2 TheJanthitrems 20

2.2.1 ProducingOrganisms 20

.2.2.2 Isolation and Chromatography of the Janthitrems 20

2.2.3 Structure of the Janthitrems 21

2.2.3.1 General Aspects, Ultraviolet and Infrared Spectroscopy. 21

2.2.3.2 Nuclear Magnetic Resonance Spectroscopy. 22

2.2.3.3 Stereochemistry of the Janthitrems : The Relative Configuration 25

2.3 TheLolitrems 25

2.3.1 Producing Organisms. 25

2.3.2 TheStructureofLolitremsBandC 25

2.3.2.1 The Stereochemistry of Lolitrem B 28

2.4 Af1atrem 28

2.4.1 Producing Organism. 28

2.4.2 The Structure of Af1atrem 28

2.5 Paxilline 30

2.5.1 ProducingOrganism 30

2.5.2 ProductionandIsolationofPaxilline 30

2.5.3 Structure of Paxilline 30

2.6 Paspaline, Paspalicine, Paspalinine and Paspalitrems A and B 32

rnn!pn!,

3E

4'

4~

4~

4~

4t

4S

4S

"I'

~-

51

51

51

~,

54

54

54

55

57

61

61

61

61

62'A

66

69

69

71

73~A

2.6.1 Producing Organism. 2.6.2 Structural Studies. : ; ,

2.7 Biosynthesis of the Penitrems. Janthitrems. Lolitrems. Aflatrem. PaxiIIine

Paspaline. Paspalicine. Paspalinine. and Paspalitrems A and B 2.8 Mode of Action of the Penitrem Type of Fungal Neurotoxins. 3. TheTerritrems 3.1 ProducingOrganisms 3.2 Isolation and Chromatography of the Territrems 3.3 Structure of the Territrems 4. Verrucosidin 4.1 Producing Organism. 4.2 StructureofVerrucosidin 5. Verruculotoxin 5.1 Producing Organism. 5.2 Isolation and Chromatography. 5.3 StructureofVerruculotoxin 5.4 Synth~sis ~.~ 6. Tremorgens Containing a 6-Methoxyindole Moiety: The Verruculogens and

Fumitremorgins 6.1 Producing Organisms. 6.2 IsolationandChromatography 6.3 Structure of Verruculogen 6.4 StructureoftheFumitremorgins 6.5 Biosynthesis of the Fumitremorgins and Verruculogen 7. TheTryptoquivalines 7,1 ProduoingOrganisms 7.2 IsolationandChromatography .

7.3 StructureofTryptoquivalineA 7.4 Structure of Nortryptoquivalone (Tryptoquivaline B or Tryptoquivalone) ...

7.5 Structures of Toxic Metabolites Related to Tryptoquivaline A and

Nortryptoquivalone. ; 7.6 Structures of Nontoxic Metabolites Related to Tryptoquivaline A and

Nortryptoquivalone. 7.7 Synthesis of the Tryptoquivalines 7.7.1 TryptoquivalineA 7.7.2 TryptoquivalineG 7.8 Biosynthesis of the Tryptoquivalines Reference.

81

82

84

Structure of Palytoxin. By R. E. MOOR]

I. Introduction II. Isolation. III. Characterization.

Contents VII

92

98

99

99

103

104

109

110

112

112

114

118

121

122

122

123

148

152

159

159

159

164

196

199

199

IV. Gross Structure Determination. ~ IV.l Periodate Oxidation. ". a) Degradation Products Implying C(1)-C(16) Segment. ..:,.,. b) Degradation Products Implying C(17)-C(27) and C(65)-C(72)

Segments. c) Degradation Products Implying C(73)-C(87) and C(98)-C(lO8)

.Segments d) Degradation Products Implying C(28)-C(64) Segment. e.)- Degradation Products Implying C(89) -C(96) Segment. b Degradation Products Implying C(lO9)-C(123) Segment. IV.2 Ozonolysis a) Degradation Products Implying C(7)-C(14) Segment. b) Degradation Products Implying C(15)-C(59) Segment. c) Degradation Products Implying C(60)-C(84) Segment. d) Degradation Products Implying C(85)-C(9l), C(92)-C(l06), !ind

C(lO7)-C(123) Segments. V. Stereochemistry V.l Methods Used for Relative Stereochemistry. a) X-Ray Crystallography. b) lHNMR Spectroscopy. c) Periodate Oxidation. d) Borate Complexation V.2 Methods Used for Absolute Stereochemistry. a) X-Ray Crystallography. b) Circular Dichroic Spectroscopy. c) Synthesis. VI. Conclusions. Acknowledgement. .

Reference!;

203

204

207

207

208

210

212

212

213

214

?1.1

Sesterterpenes: An Emerging Group of Metabolites from Marine and Terrestrial

Organisms.ByP.CREwsandS.NAYLoR I. Introduction II. Summary of Carbon Skeletons and Structural Variations. I. Conventions Table I. Sesterterpene Carbon Skeleton Classes. Table 2. Modified Sesterterpene Carbon Skeleton Classes. 2. Carbon Skeletons of "Regular" Sesterterpenes 3. Carbon Skeletons of Modified Sesterterpenes 4. Heteroatom Substituent Patterns. III. Biosynthetic and Comparative Biochemical Observations. I. Introduction. Table 3. Relationships Between Sesterterpene Carbon Skeletons and Their

OrganismSources 215

Contents"TTT

116

2U

218

219

219

225

226

227

227

228

229

229

230

232

233

233

234

258

262

?(;2

2. Biogenesis 3. Biomimetic Synthesis. 4. ComparativeBiochemistry IV. Synthesis and Biological Activity. 1. Synthesis. 2. Biological Activity. , ' Table 4. Summary of Sesterterpenes with Biological Activity. .

V. Spectroscopic Analysis. 1. Introducticn 2. A~yclic Sestert~enes Table 5. Methyl Chemical Shifts for Tri-Substituted Double Bond Isomers

3. Monocarbocyclic Sesterterpenes. 4. Tri- and Tetracarbocyclic Sesterterpenes 5. PentacarbocyclicSesterterpenes ; 6. Absolute Stereochemistry. VI. Physical and Spectroscopic Tables. 1. Table 6. Summary of Structures and Carbon-13 NMR Chemical Shifts. ..

2. Table 7. Physical Properties. Acknowledgement. References.

?71Author Index

77RSlIhip{,t. Index

l

Contents

VIIIT j~t of Contributors

1

2

2

3

5

5

10

14

17171823

25252632

373739

41414J47

52

57

58

60

63

Naturally Occurring Isocoumarins. By R.A. HILL. I. Introduction. II. Nomenclature and Structural Types. III. StructureDetermination IV.Synthesis V.Biosynthesis VI. Biological Activity. VII.lntroductiontotheTables Table 1. Isocoumarins with no 8-Oxygenation Table 2. Isocoumarins with 8-Oxygenation (a) With no Carbon Substituent at C-3 (b) With a One-Carbon Substituent at C-3 (c) With a Substituent at C-3 Containing More than One Carbon.

Table 3. Isocoumarins with 6,8-Dioxygenation (a) With no Carbon Substituent at C-3 (b) With a One-Carbon Substituent at C-3 (c) With a Substituent at C-3 Containing More than One Carbon.

Table 4. Isocoumarins with 6,7,8- Trioxygenation {a) With a One-Carbon Substituent at C-3 (b) With a Substituent at C-3 Containing More than One Carbon.

Table 5. Isocoumarins with Fused Carbocyclic Rings. (a)3,4-Fused (b)4,5-Fused (c)6,7-Fused Table 6. Isocoumarins with Nitrogen-Containing Substituents Forrl1ula Index. TrivialNamelndex Sourcelndex R..f n'

VI Contents

79Anthraquinones in the Rubiaceae. By R. WUNSMA and R. VERPOORTE

79

80

81

83

84

84

85

85

86

91

131

143

I. Introduction. , .

II.BiologicalActivity III. Biosynthesis. IV. Spectroscopy. 1. UV Spectroscopy. 2.IRSpectroscopy 3. Mass Spectrometry 4.1H-NMRSpectroscopy 5. 13C-NMR Spectroscopy. V.Artifacts VI. Separation Methods. VII. Physical and Spectroscopic Properties of Anthraquinones (Table 7)

VIII. Rubiaceae Species Containing Anthraquinones (Table 8) References.

Recent Developments in the Field of Marine Natural Products with Emphasis on Biologi-

cally Active Compounds. By H.CHR. KREBS 151

152

153154157183190193194199202203205

208208211213216216222248

253

I. Introduction. II.Porifera II.1. Steroids from Porifera II.2. Terpenoid Constituents from Porifera II.3. Amino Acid Derived Metabolites from Porifera II.4. Peptide Alkaloids, Peptides, and Proteins from Porifera ..

II.5. Nucleosides from Porifera II.6. Alkaloids and Other Heterocyclic Compounds from Porifera

II. 7. Macrolides from Porifera II.8. Phenols and .Aromatic Ethers from Porifera II.9. Carboxylic Acids from Porifera II.10. Miscellaneous Other Compounds from Porifera III. Coelenterata (Cnidaria) 111.1. Hydrozoa, Cubozoa, and Scyphozoa 111.2. Hexacorallia: Sea Anemones. 111.3. Hexacorallia: Other Organisms. 1II.4.Octocorallia 111.4.1. Steroids from Octocorallia 111.4.2. Terpenes from Octocorallia 111.4.3. Miscellaneous Compounds from Octocorallia ...

IV.Bryozoa

Contents VII

V. Mollusca. 257V.1. Gastropoda , 257

V.1j.Nudibranchia 257V.1.1.1. Steroids from Nudibrancliia 261Vj.1.2.TerpenesfromNudibranchia 261V.1.1.3. Miscellaneous Compounds from Nudibranchia ...267

V.1.2.Aplysiidae 269V.1.2.1. Terpenes from Aplysiidae 269V.1.2.2. Miscellaneous Compounds from Aplysiidae 271

V.1.3.Conidae 273V.1.4. Miscellaneous Compounds from Other Marine Snails. ...275

V.2. Bivalvia 282V.3. Cephalopoda 282

VI. Echinodermata. 282VI.1. Saponins from Starfish. 283VI.2. Steroids from Starfish. 295VI.3. Miscellaneous Compounds from Starfish. 298VI.4. Saponins from Sea Cucumbers. 299VI.5. Steroids from Sea Cucumbers. 307VI.6. Crinoids and Ophiuroids 307VI.7.SeaUrchins 308

VII. Tunicata 309

VIII. Miscellaneous Other Sources. 317

References. 320

Author Index. 365SubjectIndex 385

Contents


1The Irones andTheir Precursors. By. L. JAENICKE and F.-J. MARNER .

I. Introduction. II. Isolation and Structure Determination. III. Structure of the Irone Precursors. IV. Stereochemistry of the Iridals and the Irones Derived from Them

V. Minor Triterpenoids in [ris Extracts. VI. BiogenesisoftheIridals VII. Mechanism of Irone Ring Formation. VIII. Biological Significance of the Compounds. References.

22

23

24

The Condylocarpine Group of Indole Alkaloids. By M. LotINASMAA and P. SOMERSAW 27

1.Introduction 28

2. Structures. 29

2.1.Precondylocarpine 292.2. Condylocarpines 29

2.3.Dihydrocondylocarpines 302.4. Tubotaiwinal 30

2.5.Aspidospermatidines 312.6. 19,20-Dihydroaspidospermatine 31

2.7. Geissovelline 32

2.8. Dichotines 33

3.IsolationandOccurrence 33

3.1.Isolation 33

3.2. Occurrence. 33

4. Biogenesis. 37

5. Chemistry. 38

5.1. Correlation of Alkaloid Structures. 38

5.1.1. Precondylocarpine and Condylocarpine 38

5.1.2. Tubotaiwine 38

5.1.3.N-oxides 40

VI Contents

40414243434747

484848505051

52

52

5.1.4. Aspidospermatidines 5.1.5. Geissovelline and Dichotine 5.1.6. Further Alkaloids from Precondylocarpine

5.2.TotalSyntheses 5.2.1.Condyfoline 5.2.2. Tubotaiwine 5.2.3. Condylocarpine 6. Physical Properties. 6.1. X-ray Crystallography. 6.2. 13C NMR Spectroscopy. 6.3. lH NMR Spectroscopy. 6.4. Mass Spectrometry 6.5.0therSpectra 7. Pharmacology. References

57

58

60

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67

67

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70

72

72

73

73.'A

74

74

75

77

77

77

80

81

86

92

95

95

96

100

101

101

11)?

The Antibiotics of the Pluramycin Group (4H-Anthra[1,2-b]pyran Antibiotics).

By U. SEQUIN. 1.Introduction 2. General Structural Characteristics and Nomenclature. 3. The Families of Pluramycin Antibiotics. 3.1. Pluramycin A and Neopluramycin 3.2. Kidamycin and Isokidamycin 3.3. Hedamycin 3.4. The Rubiflavins and Rubiflavinones 3.5. Largomycin FII Chromophore Constituents. 3.6.PD121,222 3.7.Chromoxymycin 3.8.TheGriseorubins 3.9. The Indomycins and Indomycinones 4.ChemicalProperties 4.1.SeparationTechniques 4.1.1. Preparative Separations. 4.1.2. Analytical Separations. 4.2. Spectroscopy. 4.2.1.UV/VISSpectra 4.2.2. IR Spectra. 4.2.3.1H-NMRSpectra 4.2.4.13C-NMRSpectra 4.2.5. Mass Spectra. 4.3.ChemicalReactivity 4.3.1. General Chemical Characterization. 4.3.2. Degradation, Decomposition. 4.3.3. Derivatization 4.4. Stereochemistry 4.4.1.Configuration 4.4.2. Conformations.

Contents VII

105

105

107

107

107

109

109

111

111

112

113

113

116

116

117

5. Total Synthesis. 5.1.Pluramycinones 5.2.SugarMoieties 5.3. PluramycinAntibiotics 6.Biosynthesis 7. Biological and Biochemical Behaviour 7.1.GeneralRemarks 7.2. Toxicity. 7.3. Activity Against Bacteria, Yeasts and Other Microorganisms

7.4. Interaction with Phages and Lysogenic Bacteria. 7.5. Cytotoxicity. 7.6. Interaction with Nucleic Acids and Mode of Action. ..

Acknowledgement Noteaddedinproof References.

124124125126

126131132134137137

138

139

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144144144145145146

148148

Cyclosporine and Analogues -Isolation and Synthesis -Mechanism of Action

and Structural Requirements for Pharmacological Activity. By R.M. WENGER ...

I.Introduction 1.1. History and Summary. 1.2. Nomenclature. 1.3. Production ofCyclosporine 1.4. Elucidation of the Structure of Cyclosporine -Conformation of Cyclosporine

in the Crystal. 1.5. SomeChemicalModificationsofCyclosporine 1.6. Natural Cyclosporine Analogues. 1.7. Pharmacokinetics and Metabolism of Cyclosporine (1) 1.8. Elucidation of the Conformation of Cyclosporine (1) in Aprotic Solvents .

1.8.1.BackboneConformation. 1.8.2. Carbon Chains Conformations of Amino Acid Residues of Cyclospo-

rine (1) 1.8.3. Cyclosporine Conformation in Biological Fluids. 2. Monoclonal Antibodies to Cyclosporine (1) 2.1. The Antibody Response Induced by Cyclosporine 2.2. Fine Specificity of Monoclonal Antibodies. 2.3. The Conformation of Cyclosporine Seen by Antibodies in Biological Fluids

Seems to Be Similar to that Observed in Crystal. 3. The Biosynthesis of Cyclosporine 4.SynthesisofCyclosporine 4.1.Introduction 4.2. Synthesis of the Enantiomerically Pure Amino Acid MeBmt (83) 4.2.1. Synthesis of(2R,3R)-3-methyl-l,2,4-butanetriol (65) 4.2.2. Synthesis of (2R,3R,5E)-3-methyl-5-heptene-l,2-diol (71) 4.2.3. Synthesis of (2R,3R,5E)-2-hydroxy-3-methyl-5-heptenal (76) 4.2.4. Synthesis of (2S,3R,4R,6E)-3-hydroxy-4-methyl-2-(methylamino )-

6-octenoic acid (MeBmt) (83) 4.3. Strate2V Used for the Svnthesis of CvclosDorine (1)

VIII Contents

152

152

154

155

156

160

160160161162163163164

164

4.4. Cyclosporine Analogues. 4.4.1.SyntheticAnalogues 4.4.2. Semi-synthetic Analogues. : .

4.4.3. Confonnation of Cyclosporine Analogues. 5. Biological Activity and Structure-activity Relationships of Cyclosporine

Analogues. 5.1.Conclusions 6. Mechanism of Action of Cyclosporin A 6.1.Introduction 6.2. Lymphokines and the Immune System. 6.3. Importance of Interleukin-2 for Lymphocytes. 6.4. Cyclosporine and Transcriptional Control. 6.5. Membrane and Cellular Receptors. 6.6. Conclusions. References.

Biosynthesis of Iridoids and Secoiridoids. By H. INOUYE and S. UESATO 169


II. Classification of Iridoids and Secoiridoids 172

III. Mevalonoid Origin of Iridoids and Secoiridoids and Mechanism ofFormation of Iridane Skeleton from Acyclic Monoterpenes 1761. Mevalonoid Origin ofIridoids and Secoiridoids 1762. Mechanism of Formation of Iridane Skeleton from Acyclic Monoterpenes 180

IV. Biosynthetic Processes After Cyclopentane Ring Formation. 1941. Intermediacy of Deoxyloganic Acid, 8-Epideoxyloganic Acid and Loganic

Acid in Biosynthesis of Iridoids 1942. Approach to Elucidation of the Mechanism of Cyclopentane Ring

Cleavage of Loganin to Secologanin 204

V. Biosynthetic Relationships Between Groups of Secoiridoid Glycosides ...2091. Sweroside-Morroniside Type Glycosides 2092. Oeloside-10-Hydroxyoleoside Type Glycosides 212

VI. Biosynthetic Pathways of Alkaloidal Glycosides and Hydrangenosides ...2151. Biosynthesis of Alkaloidal Glycosides and the Role of Strictosidine and

Deacetylisoipecoside in the Biosynthesis of Alkaloids. 2152. Biogenesis of Hydrangenosides 220

VII. Epilogue. 221

ListofCompounds. 224

References 226

237

247

Author Index

Subject Index

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