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.
Contents. -Table des matieres.
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
Literaturverzeichnis 316
Namenverzeichnis. Index of Names. Index des Auteurs. 323
Sachverzeichnis. Index of Subjects. Index des Matieres . 339
.
Inhaltsverzeichnis.
Contents. -Table des matieres.
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
I. Introduction. 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
I. Introduction. 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
I. Introduction. 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.
Contents. -Table des matieres.
,
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
Literaturverzeichnis. 138
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
Literaturverzeichnis. 192
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.
I. Introduction. 207
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.
Contents. -Table des matieres.
}
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
Literaturverzeichnis. 169
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
I. Introduction. 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
I. Introduction. 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
I. Introduction. 191
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.
Literaturverzeichnis 279
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
Literaturverzeichnis. 315
~
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
Literaturverzeichnis. 46
,
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
VIII Inhaltsverzeichnis -Contents
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
Literaturverzeichnis. 42
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.
VIII Inhaltsverzeichnis -Contents
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.
Namenverzeichnis. Author Index
Sachverzeichnis. Subject Index
629
649
Inhaltsverzeichnis. Contents
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
Inhaltsverzeichnis. Contents
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
Namenverzeichnis. Author Index
Sachverzeichnis. Subject Index .
509
532
Inhaltsverzeichnis. Contents
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
Inhaltsverzeichnis. Contents
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
Inhaltsverzeichnis. Contents
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. :
Namenverzeichnis. Author Index
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~ ..
Inhaltsverzeichnis. Contents
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
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377
377
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-3B.7
387
387
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391
392
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402
402
406
406
408
409
409
410
410
416
416
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421
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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
Inhaltsverzeichnis. Contents
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
I. Introduction. 192
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
Ref. 547.7082 ZEC V.40
CONTENTS
List of Contributors IX
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
List of Contributors IX
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
List of Contributors IX
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
List of Contributors IX
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
67
67
67
69
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
I. Introduction. 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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