Supporting Information Sumalactones A D, Four New Curvularin-type Macrolides … · 2017-08-11 ·...

1

Supporting Information

Sumalactones A−D, Four New Curvularin-type Macrolides from a

Marine Deep Sea Fungus Penicillium Sumatrense

Yue-Hua Wu,‡a Zhi-Han Zhang,‡a Yue Zhong, ‡a Jun-Jun Huang,b Xiao-Xia Li,a Jin-Yan Jiang, a Yin-

Yue Deng,a,c Lian-Hui Zhang,a and Fei He*a

aIntegrative Microbiology Research Centre, College of Agriculture, South China

Agricultural University, Guangzhou 510642, People’s Republic of China

bPharmaceutical Research Center, School of Pharmacology, Guangzhou Medical

University, Guangzhou 510182, People’s Republic of China

cGuangdong Innovative and Entrepreneurial Research Team of Sociomicrobiology

Basic Science and Frontier Technology, South China Agricultural University,

Guangzhou 510642, People’s Republic of China

‡These authors have contributed equally to this work.

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2017

2

CONTENTS1. The NMR data assignments of 1−4 .........................................................................3S2. Preparation of (S)- and (R)- MTPA esters of 1and 3 ...............................................7Figure S1. HRESIMS spectrum of 1 .............................................................................8Figure S2.1H NMR spectrum of 1 in CD3OD (500 MHz) ............................................9Figure S3.13C NMR spectrum of 1 in CD3OD (125 MHz) .........................................10Figure S4.1H-1H COSY spectrum of 1 in CD3OD......................................................11Figure S5. HSQC spectrum of 1 in CD3OD................................................................12Figure S6. HMBC spectrum of 1 in CD3OD...............................................................13Figure S7. HRESIMS spectrum of 2 ...........................................................................14Figure S8.1H NMR spectrum of 2 in CD3OD (500 MHz) ..........................................15Figure S9.13C NMR spectrum of 2 in CD3OD (125 MHz) .........................................16Figure S10.1H-1H COSY spectrum of 2 in CD3OD....................................................17Figure S11. HSQC spectrum of 2 in CD3OD..............................................................18Figure S12. HMBC spectrum of 2 in CD3OD.............................................................19Figure S13. HRESIMS spectrum of 3 .........................................................................20Figure S14.1H NMR spectrum of 3 in CD3OD (500 MHz) ........................................21Figure S15.13C NMR spectrum of 3 in CD3OD (125 MHz) .......................................22Figure S16.1H-1H COSY spectrum of 3 in CD3OD....................................................23Figure S17. HSQC spectrum of 3 in CD3OD..............................................................24Figure S18. HMBC spectrum of 3 in CD3OD.............................................................25Figure S19. HRESIMS spectrum of 4 .........................................................................26Figure S20.1H NMR spectrum of 4 in CD3OD (500 MHz) ........................................27Figure S21. 13C NMR spectrum of 4 in CD3OD (125 MHz) ......................................28Figure S22.1H-1H COSY spectrum of 4 in CD3OD....................................................29Figure S23. HSQC spectrum of 4 in CD3OD..............................................................30Figure S24. HMBC spectrum of 4 in CD3OD.............................................................31

3

S1. The NMR data assignments of 1−4

HO

OH O

OH

1

234

56

78 9

1011

1314

15 16OO 1

12

Table S113C NMR (125 MHz) and 1H NMR (500 MHz) data of 1 in CD3ODNo. δC, mult. δH (J in Hz) 1H-1H COSY HMBC1 171.8, qC2 41.3, CH2 3.44, d (18.3), a H-2b C-1, 3, 4, 8

3.96, d (18.4), b H-2a C-1, 3, 4, 5, 7, 83 136.3, qC4 110.6, CH 6.12, d (1.8) H-6 C-2, 5, 6, 85 161.0, qC6 102.4, CH 6.24, d (2.0) H-4 C-4, 5, 7, 8, 97 158.8, qC8 122.6, qC9 211.6, qC10 46.7, CH2 2.70, m, a H-10b, 11 C-9, 11,12

3.06, m, b H-10a, 11 C-9, 11, 1211 23.4, CH2 1.87, m H-10a, 10b, 12a, 12b C-9, 10, 12, 1312 35.4, CH2 1.47, overlapped, a H-11, 12b, 13 C-10

1.95, m, b H-11, 12a, 13 C-1013 76.3, CH 4.91, m H-12a, 12b, 14a, 14b C-1, 1214 45.3, CH2 1.47, overlapped, a H-13, 14b, 15 C-12, 13, 15, 16

1.70, ddd (6.6, 7.5, 14.1), b H-13, 14a, 15 C-12, 13, 15, 1615 65.5, CH 3.69, m H-14a, 14b, 16 C-13, 1416 23.9, CH3 1.12, d (6.2) H-15 C-14, 15

4

HO

OH O2

1

23

4

56

78 9

1011

12

1314

15 16OO

OH

Table S213C NMR (125 MHz) and 1H NMR (500 MHz) data of 2in CD3ODNo. δC, mult. δH (J in Hz) 1H-1H COSY HMBC1 172.7, qC2 41.3, CH2 3.49, d (18.5), a H-2b C-1, 3, 4, 8

3.98, d (18.4), b H-2a C-1, 3, 4, 5, 7, 83 136.2, qC4 110.6, CH 6.13, d (1.6) H-6 C-2, 5, 6, 85 161.0, qC6 102.4, CH 6.24, d (2.0) H-4 C-4, 5, 7, 8, 97 158.9, qC8 122.6, qC9 211.5, qC10 46.6, CH2 2.70, ddd (2.1, 7.7, 15.9), a H-10b, 11 C-9, 11,12

3.06, ddd (2.2, 10.5, 15.4), b H-10a, 11 C-9, 11, 1211 23.4, CH2 1.87, overlapped H-10a, 10b, 12a, 12b C-9, 10, 12, 1312 36.3, CH2 1.47, overlapped, a H-11, 12b, 13 C-11

1.87, overlapped, b H-11, 12a, 13 C-1113 76.3, CH 4.90, m H-12a, 12b, 14a, 14b C-1, 1514 45.9, CH2 1.47, overlapped, a H-13, 14b, 15 C-12, 13, 15, 16

1.56, ddd (3.8, 7.9, 14.2), b H-13, 14a, 15 C-12, 13, 15, 1615 65.1, CH 3.65, m H-14a, 14b, 1616 23.6, CH3 1.09, d (6.2) H-15 C-14, 15

5

1

23

4

5

67 8 9 10

11

1213

14 15 16

HO

OH O3

OOOH

H

Table S313C NMR (125 MHz) and 1H NMR (500 MHz) data of 3in CD3ODNo. δC, mult. δH (J in Hz) 1H-1H COSY HMBC1 172.4, qC2 41.1, CH2 3.46, d (17.2), a H-2b C-1, 3, 4, 8

4.14, d (17.1), b H-2a C-1, 3, 4, 7, 83 136.3, qC4 111.5, CH 6.16, d (2.2) H-6 C-2, 5, 6, 8, 95 160.9, qC6 102.6, CH 6.25, d (2.2) H-4 C-4, 5, 7, 8, 97 158.8, qC8 122.0, qC9 209.8, qC10 41.7, CH2 2.87, ddd (3.4, 6.1, 17.5), a H-10b, 11a, 11b C-9, 11,12

3.17, ddd (3.1, 11.6, 17.4), b H-10a, 11a, 11b C-9, 11, 1211 23.9, CH2 1.47, overlapped, a H-10a, 10b, 11b, 12a, 12b C-9, 10, 12, 13

1.89, m, b H-10a, 10b, 11a, 12a, 12b C-9, 10, 12, 1312 22.0, CH2 1.23, m, a H-11a, 11b, 12b, 13a, 13b C-10 ,11, 13, 14

1.66, m, b H-11a, 11b, 12a, 13a, 13b C-10, 11, 13, 1413 26.1, CH2 1.47, overlapped,a H-12a, 12b, 13b, 14a, 14b C-12, 14, 15

1.75, m, b H-12a, 12b, 13a, 14a, 14b C-12, 1514 79.8, CH 4.75, ddd (3.3, 5.1, 10.5) H-13a, 13b, 15 C-1, 12, 13, 15, 1615 69.4, CH 3.63, dq (5.3, 6.3) H-14, 16 C-13, 14, 1616 18.7, CH3 0.98, d (6.4) H-15 C-14, 15

6

1

23

4

5

67 8 9 10

11

1213

14 15 16

HO

OH O4

OOOH

H

Table S413C NMR (125 MHz) and 1H NMR (500 MHz) data of 4 in CD3ODNo. δC, mult. δH (J in Hz) 1H-1H COSY HMBC1 172.5, qC2 41.1, CH2 3.50, d (17.1), a H-2b C-1, 3, 4, 8

4.11, d (17.1), b H-2a C-1, 3, 4, 83 136.3, qC4 111.7, CH 6.17, d (2.2) H-6 C-2, 5, 6, 85 160.9, qC6 102.6, CH 6.24, d (2.2) H-4 C-4, 5, 7, 87 158.7, qC8 122.0, qC9 209.9, qC10 41.8, CH2 2.86, ddd (3.3, 6.0, 17.3), a H-10b, 11a, 11b C-9, 11

3.19, ddd (3.2, 11.6, 17.3), b H-10a, 11a, 11b C-9, 1111 23.9, CH2 1.47, overlapped, a H-10a, 10b, 11b, 12a, 12b C-9, 12

1.89, m, b H-10a, 10b, 11a, 12a, 12b C-9, 1212 22.1, CH2 1.23, m, a H-11a, 11b, 12b, 13a, 13b C-11, 13, 14

1.67, overlapped, b H-11a, 11b, 12a, 13a, 13b C-11, 13, 1413 26.3, CH2 1.47, overlapped, a H-12a, 12b, 13b, 14 C-11, 12

1.67, overlapped, b H-12a, 12b, 13a, 14 C-11, 1214 79.9, CH 4.78, ddd (2.7, 6.0, 10.2) H-13a, 13b, 15 C-1, 12, 13, 15, 1615 69.2, CH 3.62, p (6.4) H-14, 16 C-13, 14, 1616 18.9, CH3 1.02, d (6.5) H-15 C-14, 15

7

S2. Preparation of (S)- and (R)- MTPA esters of 1 and 3A solution of 1/3(1.0 mg) in pyridine-d5 (0.5 mL) was treated with (S)-MTPA chloride (15μL)

under an atmosphere of nitrogen in an NMR tube. The mixture was stirred at room temperature for

4 h to obtain the (R)-MTPA ester (1b/3b). The same procedure was used to prepare the (S)-MTPA

ester (1a/3a) with (R)-MTPA chloride.

The key ∆δ values (∆δH-11: +0.12, +0.18; ∆δH-12: +0.07, +0.12; ∆δH-13: +0.15; ∆δH-14: +0.07,

+0.07; ∆δH-16: -0.07) of the (S)- and (R)-MTPA esters of 1 (1a and 1b) indicated the S

configuration for C-15 in 1.

The key ∆δ values (∆δH-11: +0.16, +0.21; ∆δH-12: +0.08, +0.08; ∆δH-13: +0.01, +0.09; ∆δH-14:

+0.02; ∆δH-16: -0.10) of the (S)- and (R)-MTPA esters of 3(3a and 3b) indicated the S

configuration for C-15 in 3.

8

Figure S1. HRESIMS spectrum of 1

9

Figure S2. 1H NMR spectrum of 1 in CD3OD (500 MHz)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.5f1 (ppm)

3.18

2.33

1.27

2.13

1.09

1.07

1.06

1.06

1.19

1.15

1.41

1.03

1.00

1.1136

1.1259

1.4651

1.6684

1.7096

1.8497

1.8865

1.9343

1.9528

2.6782

2.6839

2.6924

2.6987

2.7192

3.0253

3.0564

3.3000

3.4600

3.6573

3.9393

3.9758

4.8811

4.8869

4.8943

4.9002

4.9077

4.9154

4.9211

4.9286

4.9341

6.1180

6.1217

6.2366

6.2408

10

Figure S3. 13C NMR spectrum of 1 in CD3OD (125 MHz)

0102030405060708090110130150170190210f1 (ppm)

23.41

23.85

35.43

41.34

45.30

46.69

65.54

76.25

102.39

110.58

122.65

136.26

158.78

160.95

171.85

211.56

11

Figure S4. 1H-1H COSY spectrum of 1 in CD3OD

0.00.51.01.52.02.53.03.54.04.55.05.56.06.5f2 (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

6.5

f1(ppm)

12

Figure S5. HSQC spectrum of 1 in CD3OD

0.51.52.53.54.55.56.5f2 (ppm)

0

20

40

60

80

100

120

140

160

180

200

220

f1(ppm)

13

Figure S6. HMBC spectrum of 1 in CD3OD

0.51.52.53.54.55.56.5f2 (ppm)

0

20

40

60

80

100

120

140

160

180

200

220

f1(ppm)

14


15


0.00.51.01.52.02.53.03.54.04.55.05.56.06.5f1 (ppm)

3.34

2.20

1.35

3.36

1.01

1.04

1.09

1.13

1.10

1.04

1.00

1.0808

1.0933

1.4598

1.4883

1.5527

1.8245

1.8387

1.8617

1.8803

2.6779

2.6810

2.6934

2.6966

2.7084

3.0321

3.0630

3.3001

3.4686

3.6280

3.6471

3.9628

3.9995

4.8752

4.8811

4.8843

4.8908

4.8970

4.9007

4.9060

4.9117

4.9175

6.1262

6.1295

6.2419

6.2459

16


102030405060708090110130150170190210f1 (ppm)

23.44

23.58

36.25

41.28

45.89

46.61

65.06

76.30

102.45

110.63

122.57

136.22

158.87

161.02

172.67

211.52

17


0.00.51.01.52.02.53.03.54.04.55.05.56.06.5f2 (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

6.5

f1(ppm)

18


0.00.51.01.52.02.53.03.54.04.55.05.56.06.5f2 (ppm)

0

20

40

60

80

100

120

140

160

180

200

f1(ppm)

19


0.00.51.01.52.02.53.03.54.04.55.05.56.06.5f2 (ppm)

0

20

40

60

80

100

120

140

160

180

200

f1(ppm)

20


21


0.00.51.01.52.02.53.03.54.04.55.05.56.06.5f1 (ppm)

3.21

1.24

2.27

1.16

1.14

1.07

1.06

1.10

1.09

1.18

1.08

1.09

1.05

1.00

0.9747

0.9839

1.2322

1.4321

1.6354

1.6634

1.6909

1.7435

1.7645

1.8987

2.8524

2.8572

2.8611

2.8659

2.8860

3.1501

3.1714

3.1917

3.4505

3.6132

3.6299

3.6389

4.1285

4.1529

4.7380

4.7427

4.7452

4.7500

4.7531

4.7577

4.7603

4.7650

6.1562

6.1594

6.2439

6.2471

22


0102030405060708090110130150170190210f1 (ppm)

18.75

22.01

23.86

26.06

41.11

41.70

69.38

79.80

102.57

111.48

122.00

136.30

158.79

160.89

172.38

209.83

23


0.00.51.01.52.02.53.03.54.04.55.05.56.06.5f2 (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

6.5

f1(ppm)

24


0.00.51.01.52.02.53.03.54.04.55.05.56.06.5f2 (ppm)

0

20

40

60

80

100

120

140

160

180

200

f1(ppm)

25


0.00.51.01.52.02.53.03.54.04.55.05.56.06.5f2 (ppm)

0

20

40

60

80

100

120

140

160

180

200

220

f1(ppm)

26


27


0.00.51.01.52.02.53.03.54.04.55.05.56.06.5f1 (ppm)

3.24

1.18

2.49

2.55

1.28

1.06

0.91

1.15

1.57

1.04

1.24

1.05

1.00

1.0101

1.0231

1.2305

1.4407

1.4937

1.6437

1.8504

1.8656

1.8825

1.8984

1.9172

2.8354

2.8419

2.8473

2.8540

2.8700

2.8768

3.1567

3.1798

3.1913

3.4797

3.5140

3.5960

3.6088

3.6215

4.0968

4.1309

4.7561

4.7624

4.7681

4.7748

4.7765

4.7827

4.7893

4.7947

6.1660

6.1703

6.2394

6.2438

28


0102030405060708090110130150170190210f1 (ppm)

18.89

22.09

23.86

26.29

41.11

41.76

69.21

79.89

102.58

111.65

121.98

136.35

158.72

160.87

172.54

209.90

29


0.51.01.52.02.53.03.54.04.55.05.56.06.5f2 (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

6.5

f1(ppm)

30


0.51.01.52.02.53.03.54.04.55.05.56.06.5f2 (ppm)

0

20

40

60

80

100

120

140

160

180

200

220

f1(ppm)

31


0.51.01.52.02.53.03.54.04.55.05.56.06.5f2 (ppm)

0

20

40

60

80

100

120

140

160

180

200

220

f1(ppm)

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Supporting Information Sumalactones A D, Four New Curvularin-type Macrolides … · 2017-08-11 ·...

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