Supplementary Information

Transcription

1 Supplementary Information S1. Energy Minimization and ECD Calculations. Figure S1. HRESIMS spectrum of compound 1. Figure S2. IR spectrum of compound 1. Figure S3. 1 H NMR spectrum of compound 1 in CDCl 3. Figure S4. 13 C NMR spectrum of compound 1 in CDCl 3. Figure S5. DEPT spectrum of compound 1 in CDCl 3. Figure S6. HSQC spectrum of compound 1 in CDCl 3. Figure S7. 1 H- 1 H COSY spectrum of compound 1 in CDCl 3. Figure S8. HMBC spectrum of compound 1 in CDCl 3. Figure S9. NOESY spectrum of compound 1 in CDCl 3. Figure S10. HRESIMS spectrum of compound 2. Figure S11. IR spectrum of compound 2. Figure S12. 1 H NMR spectrum of compound 2 in CDCl 3. Figure S13. 1 H NMR spectrum of compound 2 in DMSO-d 6. Figure S C NMR and DEPT spectrum of compound 2 in CDCl 3. Figure S15. HSQC spectrum of compound 2 in CDCl 3. Figure S16. 1 H- 1 H COSY spectrum of compound 2 in CDCl 3. Figure S17. HMBC spectrum of compound 2 in CDCl 3. Figure S18. NOESY spectrum of compound 2 in CDCl 3. Figure S19. Partial NOESY spectrum of compound 2 in CDCl 3. Figure S20. HRESIMS spectrum of compound 3. Figure S21. IR spectrum of compound 3. Figure S22. 1 H NMR spectrum of compound 3 in CDCl 3. Figure S23. 1 H NMR spectrum of compound 3 in DMSO-d 6. Figure S C NMR and DEPT spectrum of compound 3 in CDCl 3. Figure S25. DEPT spectrum of compound 3 in CDCl 3. Figure S26. HSQC spectrum of compound 3 in CDCl 3. Figure S27. 1 H- 1 H COSY spectrum of compound 3 in CDCl 3. Figure S28. HMBC spectrum of compound 3 in CDCl 3. Figure S29. NOESY spectrum of compound 3 in CDCl 3. Figure S30. HRESIMS spectrum of compound 4. Figure S31. IR spectrum of compound 4. Figure S32. 1 H NMR spectrum of compound 4 in CDCl 3. Figure S C NMR and DEPT spectrum of compound 4 in CDCl 3. Figure S34. DEPT spectrum of compound 4 in CDCl 3. Figure S35. HSQC spectrum of compound 4 in CDCl 3. Figure S36. 1 H- 1 H COSY spectrum of compound 4 in CDCl 3. Figure S37. HMBC spectrum of compound 4 in CDCl 3. Figure S38. NOESY spectrum of compound 4 in CDCl 3. Figure S39. HRESIMS spectrum of compound 5. Figure S40. IR spectrum of compound 5.

2 S2 Figure S41. 1 H NMR spectrum of compound 5 in CDCl 3. Figure S42. 1 H NMR spectrum of compound 5 in DMSO-d 6. Figure S C NMR spectrum of compound 5 in CDCl 3. Figure S44. DEPT spectrum of compound 5 in CDCl 3. Figure S45. HSQC spectrum of compound 5 in CDCl 3. Figure S46. 1 H- 1 H COSY spectrum of compound 5 in CDCl 3. Figure S47. HMBC spectrum of compound 5 in CDCl 3. Figure S48. NOESY spectrum of compound 5 in CDCl 3. Figure S49. 1 H NMR data of MTPA esters (2S, 2R, 3S, 3R). S1. Energy Minimization and ECD Calculations The initial conformational distribution search was performed using MMFF94 method overlaid with key correlations observed in the NOESY spectra of 1. The corresponding minimum geometries were preoptimized at HF/6-31G level in Gaussian 03 program package [1,2], which was further checked by frequency calculation and resulted in no imaginary frequencies. And their minimum geometries were further optimized by DFT calculation B3LYP at g(d) level in the gas phase. The stable conformers obtained were submitted to ECD calculation by TDDFT [b3lyp/aug-cc-pvdz] method under Self-Consistent Reaction Field model of solvent (MeOH). The overall predicted ECD spectra of 1 were subsequently compared with the experimental one. S1.1. Energy Minimization of Four Possible Relative Structures of 1 (1A 1D) H HN O H O H HN O H O H HN O H O H HN O H O H H H 1A 1B 1C 1D H Formula: E = (E E 1A ) kcal/mol [2]

3 S3 1A E(RHF/6-31G(d)) = a.u. E = 0 kcal/mol Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

4 S4 1B E(RHF/6-31G(d)) = a.u. E = 72.2 kcal/mol Standard orientation: Center Number Atomic Number Atomic Type Coordinates (Angstroms) X Y Z

5 S5 1C E(RHF/6-31G(d)) = a.u. E = 70.9 kcal/mol Standard orientation: Center Number Atomic Number Atomic Type Coordinates (Angstroms) X Y Z

6 S6 1D Energetically could not exist S1.2. Standard Orientation of Two Enantiomers of 1A for ECD Calculation Optimized structure of 1a 24 4 H O H HN O Cartesian coordinate of 1a optimized: Standard orientation: H 1a (4S, 24R) Center Number Atomic Number Atomic Type Coordinates (Angstroms) X Y Z

7 S7 Optimized structure of the enantiomer 1b 24 H HN O 4 H O H Cartesian coordinate of the enantiomer 1b optimized: Standard orientation: Center Number Atomic Number Atomic Type 1b (4R, 24S) Coordinates (Angstroms) X Y Z

8 S8 Figure S1. HRESIMS spectrum of compound 1.

9 S9 Figure S2. IR spectrum of compound 1.

10 S10 Figure S3. 1 H NMR spectrum of compound 1 in CDCl NH a b

11 S11 Figure S4. 13 C NMR spectrum of compound 1 in CDCl

12 S12 Figure S5. DEPT spectrum of compound 1 in CDCl 3.

13 S13 Figure S6. HSQC spectrum of compound 1 in CDCl 3.

14 S14 Figure S7. 1 H 1 H COSY spectrum of compound 1 in CDCl 3.

15 S15 Figure S8. HMBC spectrum of compound 1 in CDCl 3.

16 S16 Figure S9. NOESY spectrum of compound 1 in CDCl 3.

17 S17 Figure S10. HRESIMS spectrum of compound 2.

18 S18 Figure S11. IR spectrum of compound 2.

19 S19 Figure S12. 1 H NMR spectrum of compound 2 in CDCl a 2b 5a b 16 12

20 S20 Figure S13. 1 H NMR spectrum of compound 2 in DMSO. NH NH OH

21 S21 Figure S C NMR and DEPT spectrum of compound 2 in CDCl

22 S22 Figure S15. HSQC spectrum of compound 2 in CDCl 3.

23 S23 Figure S16. 1 H 1 H COSY spectrum of compound 2 in CDCl 3.

24 S24 Figure S17. HMBC spectrum of compound 2 in CDCl 3.

25 S25 Figure S18. NOESY spectrum of compound 2 in CDCl 3.

26 S26 Figure S19. Partial NOESY spectrum of compound 2 in CDCl 3. NH NH

27 S27 Figure S20. HRESIMS spectrum of compound 3.

28 S28 Figure S21. IR spectrum of compound 3.

29 S29 Figure S22. 1 H NMR spectrum of compound 3 in CDCl a b

30 S30 Figure S23. 1 H NMR spectrum of compound 3 in DMSO. OH NH OH 4

31 S31 Figure S C NMR spectrum of compound 3 in CDCl

32 S32 Figure S25. DEPT spectrum of compound 3 in CDCl 3.

33 S33 Figure S26. HSQC spectrum of compound 3 in CDCl 3.

34 S34 Figure S27. 1 H 1 H COSY spectrum of compound 3 in CDCl 3.

35 S35 Figure S28. HMBC spectrum of compound 3 in CDCl 3.

36 S36 Figure S29. NOESY spectrum of compound 3 in CDCl 3.

37 S37 Figure S30. HRESIMS spectrum of compound 4.

38 S38 Figure S31. IR spectrum of compound 4.

39 S39 Figure S32. 1 H NMR spectrum of compound 4 in CDCl

40 S40 Figure S C NMR spectrum of compound 4 in CDCl

41 S41 Figure S34. DEPT spectrum of compound 4 in CDCl 3.

42 S42 Figure S35. HSQC spectrum of compound 4 in CDCl 3.

43 S43 Figure S36. 1 H 1 H COSY spectrum of compound 4 in CDCl 3.

44 S44 Figure S37. HMBC spectrum of compound 4 in CDCl 3.

45 S45 Figure S38. NOESY spectrum of compound 4 in CDCl 3.

46 S46 Figure S39. HRESIMS spectrum of compound 5.

47 S47 Figure S40. IR spectrum of compound 5.

48 S48 Figure S41. 1 H NMR spectrum of compound 5 in CDCl

49 S49 Figure S42. 1 H NMR spectrum of compound 5 in DMSO-d 6.

50 S50 Figure S C NMR spectrum of compound 5 in CDCl

51 S51 Figure S44. DEPT spectrum of compound 5 in CDCl 3.

52 S52 Figure S45. HSQC spectrum of compound 5 in CDCl 3.

53 S53 Figure S46. 1 H 1 H COSY spectrum of compound 5 in CDCl 3.

54 S54 Figure S47. HMBC spectrum of compound 5 in CDCl 3.

55 S55 Figure S48. NOESY spectrum of compound 5 in CDCl 3.

56 S56 References Figure S49. 1 H NMR data of MTPA esters (2S, 2R, 3S, 3R). 1 H NMR data of 2S (500 MHz, CDCl 3 ): δ (1H, m, H-2a), (1H, m, H-2b), (1H, m, H-4), (1H, m, H-5a), (1H, m, H-5b), (1H, br s, H-6). 1 H NMR data of 2R (500 MHz, CDCl 3 ): δ (1H, m, H-2a), (1H, m, H-2b), (1H, m, H-4), (1H, m, H-5a), (1H, m, H-5b), (1H, br s, H-6). 1 H NMR data of 3S (500 MHz, CDCl 3 ): δ (1H, m, H-2), (1H, m, H-4), (1H, m, H-5a), (1H, m, H-5b), (1H, br s, H-6). 1 H NMR data of 3R (500 MHz, CDCl 3 ): δ (1H, m, H-2), (1H, m, H-4), (1H, m, H-5a), (1H, m, H-5b), (1H, br s, H-6). 1. Frisch, M.J.; Trucks, G.W.; Schlegel, H.B.; Scuseria, G.E.; Robb, M.A.; Cheeseman, J.R.; Montgomery, J.A., Jr.; Vreven, T.; Kudin, K.N.; Burant, J.C.; et al. Gaussian 03, revision D.01; Gaussian, Inc.: Wallingford, CT, USA, Available online: (accessed on 11 December 2013) by the authors; licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution license (