Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2007

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1 Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2007

2 Wuweizidilactones A F: Novel highly oxygenated nortriterpenoids with unusual skeletons from Schisandra chinensis Sheng-Xiong Huang, Li-Bin Yang, Wei-Lie Xiao, Chun Lei, Jing-Pin Liu, Yang Lu, Zhi-Ying Weng, Li-Mei Li, Rong-Tao Li, Jun-Lin Yu, Qi-Tai Zheng, and Han-Dong Sun 1

3 Supporting Information Table S1. Detailed 2D NMR data of 3 (pyridine-d 5, 125 MHz) Position COSY (H? H) HMBC (H? C) ROESY (H? H) H-1 H-2ß C-2, 3, 10, 19 H-2ß, H-19a, H-19ß, H 3-29 H-2a H-2ß C-1, 3, 10 H-1 H-2ß H-1, H-2a C-1, 3 H-1 H-5 H-6a, H-6ß C-4, 7, 10, 29, 30 H-6a, H 3-30 H-6a H-5, H-7 C-4, 5, 7, 8 H-5, H 3-30 H-6ß H-5 C-4, 5, 8, 10 H 3-29 H-7 H-6a, H-8(weak) C-5, 6, 8, 14 and OAc H-6, H-8, H-15, H 3-18 H-8 H-7 (weak) C-9, 11, 14, 19 H-7, H 3-18 H-11a H-11ß, H 2-12 C-12, 13 H-19a H-11ß H-11a, H 2-12 C-8, 9, 12, 13, 19 H-12a H-11a, H-11ß, H-12ß C-9, 11 H-17 H-12ß H-11a, H-11ß, H-12a- C-9, 11, 13, 14 H-15 H 2-16 C-13, 17, 18 H-7, H 2-16, H 3-18 H 2-16 H-15, H-17 C-13, 14, 15, 17 H-15, 17, H 3-18, H 3-21 H-17 H-16, H-20 C-13, 14, 20, 22 H-12a, H 2-16, H-20 H 3-18 C-8, 13, 14, 15 H-7, H-8, H-15, H 2-16, H-22 H-19a H-19ß C-1, 5, 8, 9, 10 H-1, H-11a H-19ß H-19a C-1, 5, 8, 9, 10 H-1, H-20 H-17, H 3-21, H-22 C-17, 21, 22, 23 H-17, H 3-21, H-23 H 3-21 H-20 C-17, 20, 22 H 2-16, H-20, H-22, H-24 H-22 H-20, H-23 C-20, 21, 23, 24 H 3-18, H-20, H 3-21, H-24 H-23 H-22, H-24 H-20, H-24 H-24 H-23, H 3-27 C-23, 25, 27 H-22, H 3-27 H 3-27 H-24 C-24, 25, 26 H-24 2

4 H 3-29 C-4, 5, 30 H-1, H-6ß H 3-30 C-4, 5, 29 H-5, H-6a 3

5 Coordinates and optimized energies of computations (method: B3LYP/6-31G) Wuweizidilactone C (3): Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

6

7

8 The complete ref.10 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr. T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. Petersson, A. H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratemann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuk, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian 03 User s Reference Gaussian Inc. 2003, Carnegie, PA , USA. 7

9 8

10 9 ESIMS spectra of wuweizidilactone A (1)

11 10 HRESIMS spectra of wuweizidilactone A (1)

12 1 H NMR spectrum of wuweizidilactone A (1) (ppm) 11

13 13 C and DEPT NMR spectra of wuweizidilactone A (1) 12

14 (ppm)

15 HSQC spectrum of wuweizidilactone A (1) ( ppm ) ( ppm )

16 15 HMBC spectrum of wuweizidilactone A (1)

17 ( ppm ) ( ppm )

18 17 HRESIMS spectra of wuweizidilactone B (2)

19 1 H NMR spectrum of wuweizidilactone B (2) (ppm)

20 13 C and DEPT NMR spectra of wuweizidilactone B (2) (ppm)

21 HSQC spectrum of wuweizidilactone B (2) (ppm ) (ppm )

22 HMBC spectrum of wuweizidilactone B (2) ( ppm ) ( ppm )

23 ROESY spectrum of wuweizidilactone B (2) (ppm ) (ppm )

24 23 FABMS spectra of wuweizidilactone C (3)

25 24 HRESIMS spectra of wuweizidilactone C (3)

26 25 1 H NMR spectrum of wuweizidilactone C (3)

27 OAc H-19 Á Me-29 Me-30 Me-18 Me-27 H-24 OH-9 OH-15 H-7 H-23 H-1 H-15 H-22 H-12 Á H-8 H-5 H-11 Á H-17 H-20 H-6 Á H-19 Â H-2 Á H 2-16 H-11 Â H-2 Â H-6 Â Me (ppm) C and DEPT NMR spectra of wuweizidilactone C (3) 26

28 C-26 C-3 OAc C-24 C-23 C-1 C-22 C-15 C-25 C-10 C-13 C-4 C-9 C-7 C-8 C-5 C-17 C-19 C-11 C-14 C-2 C-20 C-12 C-6 C-18 C-21 C-16 C-30 C-29 OAc C (ppm) HSQC NMR spectrum of wuweizidilactone C (3) 27

29 ( ppm ) ( ppm )

30 1 H- 1 H COSY NMR spectrum of wuweizidilactone C (3) (ppm ) (ppm ) HMBC NMR spectrum of wuweizidilactone C (3) 29

31 (ppm ) (ppm ) ROESY NMR spectrum of wuweizidilactone C (3) 30

32 ( ppm ) ( ppm ) H NMR spectrum of wuweizidilactone D (4) 31

33 (ppm)

34 13 C and DEPT NMR spectra of wuweizidilactone D (4) (ppm)

35 34 HSQC NMR spectrum of wuweizidilactone D (4)

36 (ppm ) (ppm ) HMBC NMR spectrum of wuweizidilactone D (4) 35

37 (ppm ) (ppm ) H NMR spectrum of wuweizidilactone E (5) 36

38 (ppm) C and DEPT NMR spectra of wuweizidilactone E (5) 37

39 (ppm) HSQC NMR spectrum of wuweizidilactone E (5) 38

40 (ppm ) (ppm ) HMBC NMR spectrum of wuweizidilactone E (5) 39

41 (ppm ) (ppm ) ROESY NMR spectrum of wuweizidilactone E (5) 40

42 (ppm ) (ppm ) H NMR spectrum of wuweizidilactone F (6) 41

43 (ppm) C and DEPT NMR spectra of wuweizidilactone F (6) 42

44 (ppm) HSQC NMR spectrum of wuweizidilactone F (6) 43

45 (ppm ) (ppm ) HMBC NMR spectrum of wuweizidilactone F (6) 44

46 ( ppm ) ( ppm ) ROESY NMR spectrum of wuweizidilactone F (6) 45

47 (ppm ) (ppm )

48 47 1 H NMR spectrum of micrandilactone B (7)

49 ( ppm) 1 H NMR spectrum of (R)-MTPA ester of 7 48

50 (ppm) 1 H NMR spectrum of (S)-MTPA ester of 7 49

51 (ppm) COSY spectrum of (R)-MTPA ester of 7 50

52 (ppm ) (ppm ) COSY spectrum of (S)-MTPA ester of 7 51

53 ( ppm ) ( ppm )