Asperolides A C, Tetranorlabdane Diterpenoids from the Marine

Transcription

1 Supporting Information Asperolides A C, Tetranorlabdane Diterpenoids from the Marine Alga-derived Endophytic Fungus Aspergillus wentii EN-48 Hao-Fen Sun,, Xiao-Ming Li, Li Meng, Chuan-Ming Cui,, Shu-Shan Gao,, Chun-Shun Li, Cai-Guo Huang, and Bin-Gui Wang*, Key Laboratory of Experimental Marine Biology, Institute of Oceanology, Chinese Academy of Sciences, Nanhai Road 7, Qingdao , People s Republic of China, Graduate School of Chinese Academy of Sciences, Yuquan Road 19A, Beijing , People s Republic of China, and Department of Biochemistry and Molecular Biology, Second Military Medical University, Xiangyin Road 800, Shanghai , People s Republic of China * To whom correspondence should be addressed. Tel. & Fax: huangcaig@hotmail.com (C.-G.H.), wangbg@ms.qdio.ac.cn (B.-G.W.) Institute of Oceanology. Graduate School of Chinese Academy of Sciences. Second Military Medical University. 1

2 Contents S3: 1 H NMR (500 MHz, DMSO-d 6 ) spectrum of compound 1. S4: 13 C NMR (125 MHz, DMSO-d 6 ) and DEPT spectra of compound 1. S5: 1 H- 1 H COSY spectrum of the compound 1. S6: HSQC spectrum of compound 1. S7: HMBC spectrum of compound 1. S8: NOESY spectrum of compound 1. S9: 1 H NMR (500 MHz, CDCl 3 ) spectrum of compound 2. S10: 13 C NMR (125 MHz, CDCl 3 ) and DEPT spectra of compound 2. S11: 1 H- 1 H COSY spectrum of the compound 2. S12: HSQC spectrum of compound 2. S13: HMBC spectrum of compound 2. S14: NOESY spectrum of compound 2. S15: 1 H NMR (500 MHz, CD 3 OD) spectrum of compounds 3 and 7. S16: 13 C NMR (125 MHz, CD 3 OD) and DEPT spectra of compounds 3 and 7. S17: 1 H- 1 H COSY spectrum of the compounds 3 and 7. S18: HSQC spectrum of compounds 3 and 7. S19: HMBC spectrum of compounds 3 and 7. S20: NOESY spectrum of compounds 3 and 7. S21: 1 H NMR (500 MHz, acetone-d 6 ) spectrum of 1s. S22: 1 H- 1 H COSY spectrum of 1s. S23: 1 H NMR (500 MHz, acetone-d 6 ) spectrum of 1r. S24: 1 H- 1 H COSY spectrum of 1r. S25: Table S1. 1 H NMR Data for Compounds 1 8 (500 MHz, J in Hz). S26: Table S2. 13 C NMR Data for Compounds 1 8 (125 MHz). S27: Table S3. Cytotoxic Activity of Compounds 1 8 (IC 50 μm). 2

3 S3: 1 H NMR (500 MHz, DMSO-d 6 ) spectrum of compound 1. O OH O H H O Ο compound 1 3

4 S4: 13 C NMR (125 MHz, DMSO-d 6 ) and DEPT spectra of compound 1. 4

5 S5: 1 H- 1 H COSY spectrum of the compound 1. 5

6 S6: HSQC spectrum of compound 1. 6

7 S7: HMBC spectrum of compound 1. 7

8 S8: NOESY spectrum of compound 1. 8

9 S9: 1 H NMR (500 MHz, CDCl 3 ) spectrum of compound 2. 9

10 S10: 13 C NMR (125 MHz, CDCl 3 ) and DEPT spectra of compound 2. 10

11 S11: 1 H- 1 H COSY spectrum of compound 2. 11

12 S12: HSQC spectrum of compound 2. 12

13 S13: HMBC spectrum of compound 2. 13

14 S14: NOESY spectrum of compound 2. 14

15 S15: 1 H NMR (500 MHz, CD 3 OD) spectrum of compounds 3 and 7. O O H O OH H O OH H OH H OH compound 3 compound 7 15

16 S16: 13 C NMR (125 MHz, CD 3 OD) and DEPT spectra of compounds 3 and 7. 16

17 S17: 1 H- 1 H COSY spectrum of compounds 3 and 7. 17

18 S18: HSQC spectrum of compounds 3 and 7. 18

19 S19: HMBC spectrum of compounds 3 and 7. 19

20 S20: NOESY spectrum of compounds 3 and 7. 20

21 S21: 1 H NMR spectrum (500 MHz, Me 2 CO-d 6 ) of 1s. 21

22 S22: 1 H- 1 H COSY spectrum of 1s. 22

23 S23: 1 H NMR (500 MHz, Me 2 CO-d 6 ) spectrum of 1r. 23

24 S24: 1 H- 1 H COSY spectrum of 1r. 24

25 S25: Table S1. 1 H NMR Data for Compounds 1 8 (500 MHz, J in Hz) position 1 a 2 b 3 c 4 b 5 d 6 d 7 c 8 c , ddd (6.0, 1.6, 1.4) 1.89, d (14.5) 2.34, dd (14.5, 2.2) α 1.07, m β 1.70, m 6.60, d (9.8) 3.61, d (4.2) 1.54, dd (13.4, 6.9) 2.39, dd (13.5, 8.9) α 2.24 (m) β 1.07 (m) 1.19, td (13.3, 4.0) 1.72, d (13.5) , dd (10.0, 1.1) 3.46, m 1.52, m 1.86, m 6.06, dd (9.8, 5.7) 3.37, dd (4.3, 6.0) 4.12, d (7.5) α 1.51 (m) β 1.83 (m) 1.08, td (13.5, 4.0) 2.18, d (13.3) , dd (10.0, 2.0) 3.22, d (3.7) 1.08, m 1.74, m 4.41, d (5.7) 4.27, dd (5.8, 5.3) 1.81, dd (13.7, 4.9) 2.11, dd (13.3, 3.3 ) α 1.07 (m) β 1.71, m 1.52, td (12.3, 3.0) 1.92, td (10.5, 1.5) , d (5.0) 1.81, d (4.5) 1.16, dd (10.5, 4.5) 2.29, d (4.9) 2.23, d (5.3) 2.15, d (5.0) 1.96, br. s 1.48, td (13.2, 2.5) , td (4.9, 1.5) 5.00, td (4.6, 1.6) α 1.87, m β 1.46, dd (14.2, 3.2) 5.02, td (4.7, 1.6) 5.07,dd, (5.3, 8.8) 5.17, td (5.0, 1.5) 6.64, dd (10.4, 3.0) 1.89, m 2.31, m , d (4.6) 6.19, m 2.07, dd (14.2, 3.2) 6.23, d (4.6) 6.35, d (4.0) 6.35, m 5.70, dd (10.4, 3.0) 3.94, dd (21.6, 5.0) 1.72, m , m 2.24, m 2.28, d (10.7) , d (1.7) 5.74, d (1.7) 2.90, m 2.35, d (18.2) 6.00, d (1.7) 6.21,d (1.3) 5.74, d (1.5) α 2.96, m β 2.39, d (18.2) 2.43, dd (15.9, 10.8) 2.56, dd (15.9, 3.6) , d (13.5) 5.02, dt (13.5, 1.9) 4.87, d (13.6) 4.95, dt (13.6, 2.0) α 3.40, d (10.3) β 3.34, dt (10.3, 2.1) 4.89, d (13.5) 4.99, dt (13.5, 2.5) 5.12,d (13.6) 4.98,d (13.5) 4.93, d (13.0) 5.02, d (13.0) α 3.39, d (12.0) β 3.59, d (12.0) , s 1.53, s 1.24, s 1.47, s 1.06, s 1.39, s 1.30, s 1.24, s , s 1.34, s 0.84, s 1.48, s 1.35, s 1.23, s 0.73, s 0.64, s 1-OH 5.47, d (6.0) 4.13, d (3.0) a Recorded in DMSO-d 6, b Recorded in CDCl 3, c Recorded in CD 3 OD, d Recorded in acetone-d 6. 25

26 S26: Table S2. 13 C NMR Data for Compounds 1 8 (125 MHz) position 1 a 2 b 3 c 4 b 5 d 6 d 7 c 8 c , CH 31.0, CH , CH , CH 50.2, CH 40.8, CH , CH , CH , CH 51.4, CH 20.0, CH , CH 54.7, CH 64.7, CH 20.0, CH , CH , CH 52.7, CH 38.6, CH , CH 66.9, CH 37.8, CH , CH , CH , C 43.5, C 44.6, C 46.5, C 47.8, C 43.2, C 44.0, C 44.9, C , CH 47.6, CH 53.3, CH 52.3, CH 48.2, CH 49.4, CH 52.8, CH 54.6, CH , CH 71.6, CH 20.1, CH , CH 69.6, C 72.4, CH 135.9, CH 36.1, CH , CH 121.4, CH 31.0, CH , CH 121.9, CH 122.8, CH 122.8, CH 74.3, CH , C 132.0, C 88.9, C 132.7, C 131.3, C 132.9, C 86.4, C 152.3, C , C 157.9, C 50.8, CH 154.4, C 156.7, C 159.4, C 50.8, CH 51.5, CH , C 34.6, C 37.5, C 36.6, C 35.6, C 36.5, C 37.4, C 40.2, C , CH 111.4, CH 33.5, CH , CH 112.0, CH 112.8, CH 32.7, CH , CH , C 163.2, C 180.3, C 163.0, C 163.1, C 163.9, C 179.8, C 177.3, C , CH , CH , CH , CH , CH , CH , CH , C , CH , CH , CH , CH , CH , CH , CH , CH , C 176.5, C 181.0, C 179.4, C 176.1, C 181.6, C 180.8, C 180.8, C , CH , CH , CH , CH , CH , CH , CH , CH 3 a Recorded in DMSO-d 6, b Recorded in CDCl 3, c Recorded in CD 3 OD, d Recorded in acetone-d 6. 26

27 S27: Table S3. Cytotoxic Activity of Compounds 1 8 (IC 50, μm) compound HeLa HepG2 MCF-7 MDA-MB-231 NCI-H460 SMMC-7721 SW na nd na Nd na Nd nd nd /7 na na na na na na na 8 na na na na na na na 5-Fu ADM nd na: no activity; nd: not determined; positive controls: 5-Fu, fluorouracil, ADM, adriamycin. 27