bridged pentacyclic skeleton from Xylopia vielana Support ......Fig. S18 IR (KBr disc) spectrum of...

Support information for

Xylopsides AD, four rare guaiane dimers with two unique

bridged pentacyclic skeleton from Xylopia vielana

Yang-Guo Xie, ‡a Yi-Gong Guo, ‡a Guo-Jing Wu,a Sheng-Lan Zhu,a Tao-Fang Cheng,a Yu Zhang,a Shi-Kai Yan,a, * Hui-Zi Jin, * a,c and Wei-Dong Zhang* a, b, d

a Department of Natural Product Chemistry, School of Pharmacy, Shanghai Jiao Tong University, Shanghai 200240, China

b Institute of Interdisciplinary Sciences, Shanghai University of Tradictional Chinese Medicine, Shanghai 201203, China

c Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Pharmacy, Shanghai Jiao Tong University,

Shanghai 200240, China

d School of Pharmacy, Second Military Medical University, Shanghai, 200433, China

‡ These authors contributed equally.

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2018

ContentsFig. S1 1H NMR spectrum (500 MHz, Chloroform-d) of compound 1Fig. S2 13C NMR spectrum (125 MHz, Chloroform-d) of compound 1Fig. S3 DEPT spectrum (125 MHz, Chloroform-d) of compound 1Fig. S4 1H-1H COSY spectrum (500 MHz, Chloroform-d) of compound 1Fig. S5 HSQC spectrum (500 MHz, Chloroform-d) of compound 1Fig. S6 HMBC spectrum (500 MHz, Chloroform-d) of compound 1Fig. S7 NOESY spectrum (500 MHz, Chloroform-d) of compound 1Fig. S8 HR-ESI-MS spectrum of compound 1Fig. S9 IR (KBr disc) spectrum of compound 1Fig. S10 1H NMR spectrum (500 MHz, Chloroform-d) of compound 2Fig. S11 13C NMR spectrum (125 MHz, Chloroform-d) of compound 2Fig. S12 DEPT spectrum (125 MHz, Chloroform-d) of compound 2Fig. S13 1H-1H COSY spectrum (500 MHz, Chloroform-d) of compound 2Fig. S14 HSQC spectrum (500 MHz, Chloroform-d) of compound 2Fig. S15 HMBC spectrum (500 MHz, Chloroform-d) of compound 2Fig. S16 NOESY spectrum (500 MHz, Chloroform-d) of compound 2Fig. S17 HR-ESI-MS spectrum of compound 2Fig. S18 IR (KBr disc) spectrum of compound 2Fig. S19 1H NMR spectrum (500 MHz, Chloroform-d) of compound 3Fig. S20 13C NMR spe20ctrum (125 MHz, Chloroform-d) of compound 3Fig. S21 DEPT spectrum (125 MHz, Chloroform-d) of compound 3Fig. S22 1H-1H COSY spectrum (500 MHz, Chloroform-d) of compound 3Fig. S23 HSQC spectrum (500 MHz, Chloroform-d) of compound 3Fig. S24 HMBC spectrum (500 MHz, Chloroform-d) of compound 3Fig. S25 NOESY spectrum (500 MHz, Chloroform-d) of compound 3Fig. S26 HR-ESI-MS spectrum of compound 3Fig. S27 IR (KBr disc) spectrum of compound 3Fig. S28 1H NMR spectrum (500 MHz, Chloroform-d) of compound 4Fig. S29 13C NMR spectrum (125 MHz, Chloroform-d) of compound 4Fig. S30 DEPT spectrum (125 MHz, Chloroform-d) of compound 4Fig. S31 1H-1H COSY spectrum (500 MHz, Chloroform-d) of compound 4Fig. S32 HSQC spectrum (500 MHz, Chloroform-d) of compound 4Fig. S33 HMBC spectrum (500 MHz, Chloroform-d) of compound 4Fig. S34 NOESY spectrum (500 MHz, Chloroform-d) of compound4Fig. S35 HR-ESI-MS spectrum of compound 4Fig. S36 IR (KBr disc) spectrum of compound 4Fig. S37 CD spectrum of compounds 1 and 2

Fig. S38 Key1H-1H COSY and NOESY correlations of 3Fig. S39 CD spectrum of compounds 3 and 4Fig. S40 The dose inhibition curve of NO produced by compound 4. The data were obtained from three independent experiments and expressed as the means ± SEM.Fig S41 The TIC and BPC spectrum of the crude extracts from the roots of Xylopia vielana.Fig S42 The HRESIMS of compound 1Fig S43 The HRESIMS of compound 2Fig S44 The HRESIMS of compound 3Fig S45 The HRESIMS of compound 4

1.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

-500

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

6000

6500

7000

7500

8000

XYG-X-78.1.1.fid

XYG-X-78.1 1H NMR

2.92

2.98

3.00

2.95

1.68

3.17

2.95

2.90

2.99

0.92

0.85

0.99

0.99

1.09

0.81

1.44

0.77

0.96

0.92

0.99

1.00

0.9205

0.9323

0.9847

0.9980

1.3076

1.3110

1.4780

1.8153

1.8505

1.8995

1.9020

1.9384

1.9423

1.9845

2.1849

2.1905

2.1938

2.2117

2.2166

2.3575

2.3636

2.3860

2.4069

2.5614

2.5740

2.5910

2.6248

2.6501

2.6567

2.6621

2.6773

2.9205

2.9550

3.3621

3.3967

3.5106

3.5435

5.2627

Fig. S1 1H NMR spectrum (500 MHz, Chloroform-d) of compound 1

102030405060708090100110120130140150160170180190200210f1 (ppm)

-100

0

100

200

300

400

500

600

700

800

900

1000

1100

1200

XYG-X-78.1.2.fid

XYG-X-78.1 C13 NMR

14.01

19.02

22.01

22.32

22.51

22.79

23.20

27.55

28.22

29.46

30.17

47.39

50.34

52.32

54.54

62.21

62.45

73.87

127.91

131.92

133.51

140.87

142.94

143.17

145.05

174.00

203.74

204.95

206.87

Fig. S2 13C NMR spectrum (125 MHz, Chloroform-d) of compound 1

OO

O

HH

H

OO

O

HH

H

5101520253035404550556065707580859095100105110115120125130f1 (ppm)

-300

-250

-200

-150

-100

-50

0

50

100

150

200

250

300

350

400

450

XYG-X-78.1.3.fid

XYG-X-78.1 DEPT 135

14.02

19.02

22.01

22.32

22.51

22.79

23.20

27.55

28.23

29.46

30.17

47.39

50.34

52.32

62.45

73.87

127.91

Fig. S3 DEPT spectrum (125 MHz, Chloroform-d) of compound 1

0.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.4f2 (ppm)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

f1 (ppm)

XYG-X-78.1.4.ser

XYG-X-78.1 1H 1H COSY

Fig. S4 1H-1H COSY spectrum (500 MHz, Chloroform-d) of compound 1

OO

O

HH

H

OO

O

HH

H

0.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.2f2 (ppm)

10

20

30

40

50

60

70

80

90

100

110

120

f1 (ppm)

XYG-X-78.1.5.ser

XYG-X-78.1 HSQC

Fig. S5 HSQC spectrum (500 MHz, Chloroform-d) of compound 1

0.00.51.01.52.02.53.03.54.04.55.05.5f2 (ppm)

10

20

30

40

50

60

70

80

90

100

110

120

130

140

150

160

170

180

190

200

210

f1 (ppm)

XYG-X-78.1.6.ser

XYG-X-78.1 HMBC

Fig. S6 HMBC spectrum (500 MHz, Chloroform-d) of compound 1

OO

O

HH

H

OO

O

HH

H

1.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.4f2 (ppm)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

f1 (ppm)

XYG-X-78.1.7.ser

XYG-X-78.1 NOE

Fig. S7 NOESY spectrum (500 MHz, Chloroform-d) of compound 1

Fig. S8 HR-ESI-MSspectrum of compound 1

OO

O

HH

H

Fig. S9 IR (KBr disc) spectrum of compound 1

1.01.52.02.53.03.54.04.55.05.56.06.57.0f1 (ppm)

-100

0

100

200

300

400

500

600

700

800

900

1000

1100

1200

XYG-X-59.1.fid

XYG-X-59 1H NMR

3.31

3.08

2.92

3.08

3.20

2.61

1.49

2.41

1.96

2.76

1.26

0.86

1.06

1.00

0.69

1.11

1.00

0.85

0.92

0.9093

0.9229

1.0257

1.0396

1.4214

1.4462

1.4496

1.4714

1.5203

1.8898

2.0278

2.3549

2.4880

2.4902

2.4956

2.6068

2.6200

2.6361

2.9333

2.9648

2.9994

3.4092

3.4437

5.3789

6.0621


O

OOO

HOH H

H

102030405060708090100110120130140150160170180190200210f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

13000

14000

15000

XYG-X-59.2.fid

XYG-X-59 C13 NMR

14.09

14.80

17.13

17.33

19.03

20.00

21.30

21.77

22.36

22.55

22.66

23.25

24.71

26.64

27.48

28.09

28.27

29.33

29.67

31.90

40.35

46.53

47.43

52.91

53.65

60.94

61.88

73.46

76.73 CDCl3

76.99 CDCl3

77.24 CDCl3

85.06

85.54

104.11

115.04

120.35

125.11

131.86

142.10

143.17

145.29

155.38

174.14

203.78

206.82


101520253035404550556065707580859095100105110115120125f1 (ppm)

-1500

-1000

-500

0

500

1000

1500

2000

XYG-X-59.3.fid

XYG-X-59 DEPT 135

14.80

19.03

21.78

22.37

22.56

23.25

24.71

26.64

27.48

28.10

28.27

40.35

47.43

52.91

61.88

73.46

77.19 CDCl3

120.35

125.10


O

OOO

HOH H

H

O

OOO

HOH H

H

0.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.45.65.8f2 (ppm)

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

f1 (ppm)

XYG-X-59.4.ser

XYG-X-59 1H 1H COSY


0.51.01.52.02.53.03.54.04.55.05.56.0f2 (ppm)

10

20

30

40

50

60

70

80

90

100

110

120

130

f1 (ppm)

XYG-X-59.5.ser

XYG-X-59 HSQC


O

OOO

HOH H

H

O

OOO

HOH H

H

0.51.01.52.02.53.03.54.04.55.05.56.0f2 (ppm)

0

10

20

30

40

50

60

70

80

90

100

110

120

130

140

150

160

170

180

190

200

210

f1 (ppm)

XYG-X-59.6.ser

XYG-X-59 HMBC


0.51.01.52.02.53.03.54.04.55.05.56.0f2 (ppm)

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

f1 (ppm)

XYG-X-59.7.ser

XYG-X-59 NOE

Fig. S16 NOESY spectrum (500 MHz, Chloroform-d) of compound 2O

OOO

HOH H

H

O

OOO

HOH H

H

O

OOO

HOH H

H

1.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

0

500

1000

1500

2000

2500

3000

3500

4000

XYG-X-90.1.fid

XYG-X-90 1H NMR

3.35

3.23

1.38

1.61

3.07

1.26

3.28

6.46

3.30

3.11

2.12

0.93

1.20

1.17

1.42

0.76

1.08

1.06

0.99

1.04

1.00

0.8725

0.8946

0.9059

0.9193

0.9882

1.0222

1.0353

1.2373

1.2515

1.2615

1.2712

1.3672

1.3773

1.3819

1.3854

1.3902

1.3947

1.3983

1.4030

1.4114

1.4159

1.4207

1.4249

1.4324

1.4372

1.4691

1.4724

1.5604

1.5660

1.5710

1.5756

1.5871

1.5925

1.5979

1.6545

1.6582

1.7363

1.7421

1.7495

1.7562

1.7627

1.7711

1.7772

1.7835

1.7907

1.7976

1.8006

1.8045

1.8068

1.8106

1.8457

1.8480

1.8520

1.8542

1.9156

1.9198

1.9318

1.9358

1.9464

1.9507

1.9627

1.9666

2.1794

2.1849

2.1926

2.2015

2.2080

2.2173

2.2224

2.2408

2.2456

2.3564

2.3786

2.4008

2.5419

2.5708

2.5747

2.5788

2.5901

2.5983

2.6051

2.6214

2.6440

2.6594

2.6907

2.8107

2.8165

2.8274

2.8332

3.2226

3.2552

3.3159

3.3469

5.3945

5.3989

5.4032


0102030405060708090100110120130140150160170180190200210220230240f1 (ppm)

-50

0

50

100

150

200

250

300

350

400

450

500

550

600

650

700

750XYG-X-90.2.fid

XYG-X-90 C13 NMR

14.67

14.91

21.75

22.46

22.48

22.89

23.09

28.40

30.06

30.59

40.90

48.49

49.41

50.66

50.75

58.69

60.69

64.02

72.99

126.37

133.22

134.29

134.73

139.02

140.29

140.38

142.65

205.79

206.01


O

OH

H

HHH

O

OH

H

HHH

5101520253035404550556065707580859095100105110115120125130f1 (ppm)

-3500

-3000

-2500

-2000

-1500

-1000

-500

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

XYG-X-90.3.fid

XYG-X-90 DEPT 135

14.67

14.91

21.75

22.46

22.48

22.49

22.89

23.09

28.40

30.06

30.59

40.90

48.49

49.41

50.66

50.75

58.69

64.02

72.99

126.37


0.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.45.6f2 (ppm)

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

f1 (ppm)

XYG-X-90.4.ser

XYG-X-90 1H 1H COSY


O

OH

H

HHH

O

OH

H

HHH

0.51.01.52.02.53.03.54.04.55.05.5f2 (ppm)

10

20

30

40

50

60

70

80

90

100

110

120

130

f1 (ppm)

XYG-X-90.5.ser

XYG-X-90 HSQC


0.51.01.52.02.53.03.54.04.55.05.56.0f2 (ppm)

0

10

20

30

40

50

60

70

80

90

100

110

120

130

140

150

160

170

180

190

200

210

f1 (ppm)

XYG-X-90.6.ser

XYG-X-90 HMBC


O

OH

H

HHH

O

OH

H

HHH

0.20.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.45.65.8f2 (ppm)

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

f1 (ppm)

XYG-X-90.7.ser

XYG-X-90 NOE




O

OH

H

HHH

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

-1000

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

12000

13000

14000XYG-X-91.1.fid

XYG-X-91 1H NMR

6.60

4.10

3.24

3.48

3.08

2.26

1.42

1.95

1.70

2.96

3.46

2.17

2.49

2.11

1.41

1.00

1.21

1.38

1.25

0.98

0.99

1.20

1.02

1.00

1.00

0.8156

0.8252

0.8289

0.8385

0.8707

0.8843

0.8973

0.9107

0.9616

0.9751

1.0119

1.0249

1.2343

1.2426

1.2522

1.2618

1.2720

1.2755

1.2830

1.2855

1.2918

1.2960

1.4158

1.4399

1.4448

1.4690

1.5128

1.5179

1.5236

1.5331

1.5377

1.5420

1.5549

1.5587

1.6038

1.6118

1.6151

1.8003

1.8130

1.8265

1.8402

1.8528

1.9130

1.9226

1.9262

1.9297

1.9327

1.9364

1.9397

1.9430

1.9464

1.9566

1.9602

1.9702

2.0189

2.0232

2.0281

2.0328

2.0366

2.0409

2.0450

2.0498

2.0899

2.0976

2.1058

2.1143

2.1218

2.1291

2.1352

2.1587

2.2509

2.2593

2.2806

2.2889

2.3208

2.3273

2.3381

2.3447

2.3513

2.4354

2.4414

2.4465

2.4628

2.4712

2.4759

2.5881

2.6109

2.6277

2.6344

2.6417

2.6442

2.6820

2.6879

2.6987

2.7042

5.4901


0102030405060708090100110120130140150160170180190200210220230240f1 (ppm)

-50

0

50

100

150

200

250

300

350

400

450

XYG-X-91.2.fid

XYG-X-91 C13 NMR

14.22

15.11

19.28

19.89

20.71

21.18

21.85

26.05

26.45

29.58

31.57

32.53

41.23

48.24

48.28

49.36

52.59

55.16

58.42

58.97

60.98

65.67

71.12

125.07

134.88

138.67

143.46

215.97

216.12


O

OH

H

HHH

O

OH

H

HHH

101520253035404550556065707580859095100105110115120125130135f1 (ppm)

-2000

-1500

-1000

-500

0

500

1000

1500

2000

2500

3000

3500

XYG-X-91.3.fid

XYG-X-91 DEPT 135

14.22

15.12

19.28

19.89

20.71

21.19

21.85

26.05

26.45

29.58

31.57

32.53

41.23

48.23

48.27

49.36

52.59

55.16

58.42

58.97

65.67

71.11

125.07


0.51.01.52.02.53.03.54.04.55.05.5f2 (ppm)

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

f1 (ppm)

XYG-X-91.4.ser

XYG-X-91 1H 1H COSY


O

OH

H

HHH

O

OH

H

HHH

0.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.4f2 (ppm)

10

20

30

40

50

60

70

80

90

100

110

120

f1 (ppm)

XYG-X-91.5.ser

XYG-X-91 HSQC


0.51.01.52.02.53.03.54.04.55.05.5f2 (ppm)

10

20

30

40

50

60

70

80

90

100

110

120

130

140

150

160

170

180

190

200

210

220

f1 (ppm)

XYG-X-91.6.ser

XYG-X-91 HMBC


O

OH

H

HHH

O

OH

H

HHH

0.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.45.65.8f2 (ppm)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

f1 (ppm)

XYG-X-91.7.ser

XYG-X-91 NOE




O

OH

H

HHH

200 250 300 350 400

-60

-40

-20

0

20

40

60

CD

[mdg

e]

Wavelength [nm]

1 2

Fig. S37 CD spectrum of compounds 1 and 2

4

O

O

H-9a

H-7

H-10

H-1'

H-7'

NOE1H-1H COSY

Fig. S38 Key 1H-1H COSY and NOESY correlations of 4

200 250 300 350

-60

-40

-20

0

20

40

60

80

CD

[mde

g]

Wavelength [nm]

3 4

Fig. S39 CD spectrum of compounds 3 and 4

log cncentration (M )

Nitr

ite(u

m)

-6.5 -6.0 -5.5 -5.0 -4.5 -4.0 -3.50

10

20

30

40

50

4

Fig. S40 The dose inhibition curve of NO produced by compound 4. The data were obtained from three independent experiments and expressed as the means ± SEM.

(Method：0-16 min 20-45ACN;16-42 min,45-60 ACN; 42-57 min, 60-80ACN; 57-67 min,80-100 ACN; 67-70 min, 100 ACN). We have controlled the temperature during the whole isolation process. (T < 55 ºC).

7x10

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

+ESI TIC Scan Frag=135.0V 20180808-4.d

1 1

6x10

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

2.2

2.4

2.6

+ESI BPC Scan Frag=135.0V 20180808-4.d

1 1

Counts vs. Acquisition Time (min)1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69

Fig S41 The TIC and BPC spectrum of the crude extracts from the roots of Xylopia vielana.

Fig S42 The HRESIMS of compound 1



bridged pentacyclic skeleton from Xylopia vielana Support ......Fig. S18 IR (KBr disc) spectrum of...

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