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Supporting Information for
Terpenoids Produced by Actinomycetes: Isolation, Structural Elucidation and
Biosynthesis of New Diterpenes, Gifhornenolone A and B from Verrucosispora gifhornensis
Masato Shirai1, Masaaki Okuda1, Keiichiro Motohashi1, Masaya Imoto2, Kazuo Furihata3, Yoshihide Matsuo,4 Atsuko Katsuta5, Yoshikazu Shizuri5 and Haruo Seto1*
1Faculty of Applied Bioscience, Tokyo University of Agriculture, Setagaya-ku, Tokyo 156-8502, Japan 2Science and Technology, Keio University, Yokohama-shi, Kanagawa, 223-8522, Japan 3Graduate School of Agricultural and Life Sciences, University of Tokyo, Bunkyo-ku, Tokyo, 113-8657, Japan 4Marine Biotechnology Institute Co. Ltd., Heita, Kamaishi-shi, Iwate, 026-0001, Japan (Current address: Suntory Holdings Limited, R&D Planning Division, Wakayamadai, Shimamoto-cho, Mishima-gun, Osaka, 618-8503, Japan) 5Marine Biosciences, Kamaishi Research Laboratory, Kitasato University, Heita, Kamaishi, Iwate, 026-0001, Japan
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1 Table of Contents: gifhornenolone A (1) P2-12, gifhornenolone B (2) P13-20, cyperusol C (3) P21-31
Spectral Data for gifhornenolone A (1)
1 Figure S1. H-NMR spectrum (400 MHz) of gifhornenolone A (1) in CDCl3 3
13 Figure S2. C-NMR spectrum (100 MHz) of gifhornenolone A (1) in CDCl3 4
Figure S3. HSQC spectrum (500 MHz) of gifhornenolone A (1) in CDCl3 5
Figure S4. HMBC spectrum (500 MHz) of gifhornenolone A (1) in CDCl3 6
Figure S5. COSY spectrum (500 MHz) of gifhornenolone A (1) in CDCl3 7
Figure S6. NOESY spectrum (500 MHz) of gifhornenolone A (1) in CDCl3 8
Figure S7. HR-MS spectrum of gifhornenolone A (1) 9
Figure S8. IR spectrum of gifhornenolone A (1) 9
13 13 Figure S9. C-NMR spectrum (150 MHz) of gifhornenolone A (1) labeled from [1- C] glucose in CDCl3 10
13 13 Figure S10. C-NMR spectrum (150 MHz) of gifhornenolone A (1) labeled from [U- C6] glucose in CDCl3 11
2 1 Figure S1. H-NMR spectrum (400 MHz) of Compound A (1) in CDCl3
1 Figure S1. H-NMR spectrum (400 MHz) of gifhornenolone A (1) in CDCl3
17
12 CH3 15 18 11 13 16 H3C H 14 O 1 9 2 H 10 8 3 7 5 6 4
HO 19
3 4 13 Figure S2. C-NMR spectrum (100 MHz) of gifhornenolone A (1) in CDCl3
17
12 CH3 15 18 11 13 16 H3C H 14 O 1 9 2 H 10 8 3 7 5 6 4
HO 19
5 Figure S3. HSQC spectrum (500 MHz) of gifhornenolone A (1) in CDCl3
17
12 CH3 15 18 11 13 16 H3C H 14 O 1 9 2 H 10 8 3 7 5 6 4
HO 19
methylene
6 Figure S4. HMBC spectrum (500 MHz) of gifhornenolone A (1) in CDCl3
17
12 CH3 15 18 11 13 16 H3C H 14 O 1 9 2 H 10 8 3 7 5 6 4
HO 19
7 Figure S5. COSY spectrum (500 MHz) of gifhornenolone A (1) in CDCl3
17
12 CH3 15 18 11 13 16 H3C H 14 O 1 9 2 H 10 8 3 7 5 6 4
HO 19
8 Figure S6. NOESY spectrum (500 MHz) of gifhornenolone A (1) in CDCl3
17
12 CH3 15 18 11 13 16 H3C H 14 O 1 9 2 H 10 8 3 7 5 6 4
HO 19
9 Figure S7. HR-MS spectrum of gifhornenolone A (1) Figure S8. IR spectrum of gifhornenolone A (1)
17
12 CH3 15 18 11 13 16 H3C H 14 O 1 9 2 H 10 8 3 7 5 6 4
HO 19
10 13 13 Figure S9. C-NMR spectrum (150 MHz) of gifhornenolone A (1) labeled from [1- C]glucose in CDCl3
17
12 CH3 15 18 11 13 16 H3C H 14 O 1 9 2 H 10 8 3 7 5 6 4
HO 19
11 13 13 Figure S10. C-NMR spectrum (150 MHz) of gifhornenolone A (1) labeled from [U- C6]glucose in CDCl3
17
12 CH3 15 18 11 13 16 H3C H 14 O 1 9 2 H 10 8 3 7 5 6 4
HO 19
12 Spectral Data for gifhornenolone B (2)
1 Figure S11. H-NMR spectrum (500 MHz) of gifhornenolone B (2) in CDCl3 13
13 Figure S12. C-NMR spectrum (150 MHz) of gifhornenolone B (2) in CDCl3 14
Figure S13. HSQC spectrum (400 MHz) of gifhornenolone B (2) in CDCl3 15
Figure S14. HMBC spectrum (500 MHz) of gifhornenolone B (2) in CDCl3 16
Figure S15. COSY spectrum (500 MHz) of gifhornenolone B (2) in CDCl3 17
Figure S16. NOESY spectrum (500 MHz) of gifhornenolone B (2) in CDCl3 18
Figure S17. HR-MS spectrum of gifhornenolone B (2) 19
13 1 Figure S11. H-NMR spectrum (400 MHz) of gifhornenolone B (2) in CDCl3
17
12 CH3 15 18 11 13 16 H3C H 14 O 1 9 2 H 10 8 3 7 5 6 HO 4 20 19 H3C OH
14 13 Figure S12. C-NMR spectrum (100 MHz) of gifhornenolone B (2) in CDCl3
17
12 CH3 15 18 11 13 16 H3C H 14 O 1 9 2 H 10 8 3 7 5 6 HO 4 20 19 H3C OH
15 Figure S13. HSQC spectrum (400 MHz) of gifhornenolone B (2) in CDCl3
17
12 CH3 15 18 11 13 16 H3C H 14 O 1 9 2 H 10 8 3 7 5 6 HO 4 20 19 H3C OH
16 Figure S14. HMBC spectrum (500 MHz) of gifhornenolone B (2) in CDCl3
17
12 CH3 15 18 11 13 16 H3C H 14 O 1 9 2 H 10 8 3 7 5 6 HO 4 20 19 H3C OH
17 Figure S15. COSY spectrum (500 MHz) of gifhornenolone B (2) in CDCl3
17
12 CH3 15 18 11 13 16 H3C H 14 O 1 9 2 H 10 8 3 7 5 6 HO 4 20 19 H3C OH
18 Figure S16. NOESY spectrum (500 MHz) of gifhornenolone B (2) in CDCl3
17
12 CH3 15 18 11 13 16 H3C H 14 O 1 9 2 H 10 8 3 7 5 6 HO 4 20 19 H3C OH
19 Figure S17. HR-MS spectrum of gifhornenolone B (2)
17
12 CH3 15 18 11 13 16 H3C H 14 O 1 9 2 H 10 8 3 7 5 6 HO 4 20 19 H3C OH
20 Figure S9. HR-MS spectrum of OxaloterpinFigure AS10. (1) HR-MS spectrum of Oxaloterpin A (1)
Spectral Data for cyperusol C (3)
1 Figure S18. H-NMR spectrum (400 MHz) of cyperusol C (3) in CDCl3 21
13 Figure S19. C-NMR spectrum (100 MHz) of cyperusol C (3) in CDCl3 22
Figure S20. HSQC spectrum (500 MHz) of cyperusol C (3) in CDCl3 23
Figure S21. HMBC spectrum (500 MHz) of cyperusol C (3) in CDCl3 24
Figure S22. COSY spectrum (500 MHz) of cyperusol C (3) in CDCl3 25
Figure S23. NOESY spectrum (500 MHz) of cyperusol C (3) in CDCl3 26
Figure S24. HR-MS spectrum of cyperusol C (3) 27
13 13 Figure S25. C-NMR spectrum (100 MHz) of cyperusol C (3) labeled from [1- C] glucose in CDCl3 29
13 13 Figure S26. C-NMR spectrum (100 MHz) of cyperusol C (3) labeled from [U- C6] glucose in CDCl3 30
21 1 Figure S18. H-NMR spectrum (400 MHz) of cyperusol C (3) in CDCl3
HO 14 1 CH3 9 2 10 8 H 7 11 3 4 6 5 12 H3C OH 15 CH3 13
22 13 Figure S19. C-NMR spectrum (100 MHz) of cyperusol C (3) in CDCl3
HO 14 1 CH3 9 2 10 8 H 7 11 3 4 6 5 12 H3C OH 15 CH3 13
23 Figure S20. HSQC spectrum (500 MHz) of cyperusol C (3) in CDCl3
HO 14 1 CH3 9 2 10 8 H 7 11 3 4 6 5 12 H3C OH 15 CH3 13
24
Figure S21. HMBC spectrum (500 MHz) of cyperusol C (3) in CDCl3
HO 14 1 CH3 9 2 10 8 H 7 11 3 4 6 5 12 H3C OH 15 CH3 13
25 FigureFigure S1 4S1. COSY2. COSY spectrum spectrum (500 (500 MHz) MHz) of (3ofR cypersol)-3-chloro-6-hydroxy-8-methoxy- C (2) in CDCl3 α - lapachone (8) in CDCl3
Figure S22. COSY spectrum (500 MHz) of cyperusol C (3) in CDCl3
HO 14 1 CH3 9 2 10 8 H 7 11 3 4 6 5 12 H3C OH 15 CH3 13
26 Figure S23. NOESY spectrum (500 MHz) of cyperusol C (3) in CDCl3
HO 14 1 CH3 9 2 10 8 H 7 11 3 4 6 5 12 H3C OH 15 CH3 13
27 Figure S24. HR-MS spectrum of cyperusol C (3)
HO 14 1 CH3 9 2 10 8 H 7 11 3 4 6 5 12 H3C OH 15 CH3 13
28 Figure S25. 13C-NMR spectrum (100 MHz) of cyperusol C (3)
13 labeled from [1- C]glucose in CDCl3
HO 14 1 CH3 9 2 10 8 H 7 11 3 4 6 5 12 H3C OH 15 CH3 13
29 Figure S26. 13C-NMR spectrum (100 MHz) of cyperusol C (3)
13 labeled from [U- C6]glucose in CDCl3
HO 14 1 CH3 9 2 10 8 H 7 11 3 4 6 5 12 H3C OH 15 CH3 13
30