¹H NMR Handbook of Natural Products. Volume 6: Steroids, Tropolones, Cerebrosides, Marine Natural Products, Amino Acids, and Sugars [6] 9783110630817

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Hailin Qin, Dequan Yu 1 H NMR Handbook of Natural Products

Also of Interest Volume 1: Alkaloids Hailin Qin, Dequan Yu, 2021 ISBN 978-3-11-062434-2, e-ISBN (PDF) 978-3-11-062729-9, e-ISBN (EPUB) 978-3-11-062471-7

Volume 2: Saponins Hailin Qin, Dequan Yu, 2021 ISBN 978-3-11-063074-9, e-ISBN (PDF) 978-3-11-063155-5, e-ISBN (EPUB) 978-3-11-063101-2

Volume 3: Flavones, Quinones, Phenylpropanoids, and Stilbenes Hailin Qin, Dequan Yu, 2021 ISBN 978-3-11-063077-0, e-ISBN (PDF) 978-3-11-063157-9, e-ISBN (EPUB) 978-3-11-063089-3

Volume 4: Monoterpenoids and Sesquiterpenoids Hailin Qin, Dequan Yu, 2021 ISBN 978-3-11-063078-7, e-ISBN (PDF) 978-3-11-063159-3, e-ISBN (EPUB) 978-3-11-063102-9

Volume 5: Diterpenoids, Triterpenoids, Sesterterpenoids, Tetraterpenoids, and Carotenoids Hailin Qin, Dequan Yu, 2021 ISBN 978-3-11-063110-4, e-ISBN (PDF) 978-3-11-063472-3, e-ISBN (EPUB) 978-3-11-063145-6

Hailin Qin, Dequan Yu

1

H NMR Handbook of Natural Products |

Volume 6: Steroids, Tropolones, Cerebrosides, Marine Natural Products, Amino Acids, and Sugars

Authors Prof. Dr. Hailin Qin Institute of Materia Medica Chinese Academy of Medical Sciences and Peking Union Medical College Beijing China [email protected]

Prof. Dequan Yu Academician of Chinese Academy of Engineering Institute of Materia Medica Chinese Academy of Medical Sciences and Peking Union Medical College Beijing China [email protected]

ISBN 978-3-11-063081-7 e-ISBN (PDF) 978-3-11-063161-6 e-ISBN (EPUB) 978-3-11-063092-3 Library of Congress Control Number: 2021931822 Bibliographic information published by the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at http://dnb.dnb.de. © 2021 Chemistry Industry Press and Walter de Gruyter GmbH, Berlin/Boston Cover image: KirsanovV / iStock / Getty Images Plus Typesetting: VTeX UAB, Lithuania Printing and binding: CPI books GmbH, Leck www.degruyter.com

Contents List of Participants | VII 13 Steroids | 1 13.1 Common steroids | 1 13.1.1 Androstane-type steroids | 1 13.1.2 Pregnane-type steroids | 2 13.1.3 Cardica glycosides | 8 13.1.4 Cholestane-type steroids | 13 13.1.5 Ergostane-type steroids | 14 13.1.6 Ergoline-type steroids | 16 13.2 Some additional steroids | 20 14 14.1 14.2

Tropolones and cerebrosides | 33 Tropolones | 33 Cerebrosides | 38

15 Marine natural products | 49 15.1 Marine terpenoids | 49 15.2 Marine steroids | 79 15.2.1 Marine pregnane-type steroids | 79 15.2.2 Marine cholestane-type steroids | 82 15.2.3 Marine ergostane-type steroids | 94 15.2.4 Marine stigmastane-type steroids | 107 15.2.5 Some additional marine steroids | 113 15.3 Marine alkaloids | 134 15.4 Some additional marine natural products | 153 16 16.1 16.2

Amino acids and sugars | 169 Amino acids | 169 Sugars | 175

Index of compound names | 179 Index of molecular formula of compounds | 187

List of Participants Editors in Chief: H.-L. Qin, D.-Q. Yu Deputy Editors in Chief: A.-J. Deng, R.-Y. Yan, Q.-J. Zhang Participants: J.-Q. Yu, Q. Zhou, Z.-Y. Hao, D. Liang, T. Sun, Z.-H. Zhang, Y. Yue, H.-L. Long, W. Zhao, D. Zhang

13 Steroids 13.1 Common steroids 13.1.1 Androstane-type steroids Table 13-1-1: Compounds, MFs, and test solvents of androstane-type steroids 13-1-1 and 13-1-2. No.

Compounds

MFs

Test solvents

References

13-1-1 13-1-2

6α-hydroxyandrosta-1,4-diene-3,17-dione 2α,3α-dihydroxyandrostan-16-one-2β,19-hemiketal

C19 H24 O3 C19 H28 O4

CDCl3 C5 D5 N

[1] [2]

Table 13-1-2: 1 H NMR spectroscopic data of androstane-type steroids 13-1-1 and 13-1-2. H

13-1-1

13-1-2

H

13-1-1

13-1-2

1

6.99 d(10.0)

11

6.48 dd(1.9, 10.3)

1.65 m 1.83 m 1,26 m, 1.85 m 1.29 m 1.59 m, 1.96 m

β 1.35

2 3 4

α 2.40 d(10.8) β 2.30 d(10.4)

6.22 t(1.8)

5

4.38 m α 2.01

12 14 15

β 1.85 1.30

16

6

4.49 ddd(1.7, 5.5, 11.7)

7 8

1.10 m 2.33 ddd(3.7, 5.5, 12.0) 1.85 m

α 1.55 β 1.20 α 1.28 β 1.43 0.85

9

1.07 m

1.18

https://doi.org/10.1515/9783110631616-013

17

2.07 dd(10.0, 19.0) 2.45 dd(9.0,19.0)

18

0.91 s

19

1.21 s

1.60 1.27 α 2.15 dd(7.6, 18.0) β 1.83

α 1.92 d(16.8) β 2.06 d(16.8) 0.66 s 4.10 d(8.0), 3.89 d(8.0)

2 | 13 Steroids 13.1.2 Pregnane-type steroids Table 13-1-3: Compounds, MFs, and test solvents of pregnane-type steroids 13-1-3∼13-1-25. No.

Compounds

MFs

Test solvents

References

13-1-3 13-1-4 13-1-5

vladimuliecin A vladimuliecin B (3R,5R,6R,8S,9R,10R,13R,14R,17S,20R)-3,5-cyclopregnane-6,8,14,20-tetraol pregna-5,14-dienolone-3-O-sulfate allo-pregna-5,14-dienolone-3-O-sulfate 14β-hydroxypregn-5-enolone-3-O-sulfate stizophyllin terresterone A terresterone B pregna-5,20-diene-3α,7α-diol 3α-acetate pregna-5,20-diene-3β,7α-diol 7α-acetate pregna-5,20-dien-3β-ol pregna-5,20-diene-3α,7α,11α-triol-3α-acetate pregna-5,20-diene-3α,7α,11α-triol-3α,7α-diacetate pregna-5,20-diene-3α,7α,19-triol-3α,19-diacetate pregna-5,20-diene-3α,7α,11α,19-tetrol-3α,7α,19triacetate (E)-aglawone aglatomin A aglatomin B 16-β-acetyloxy-pregn-4-17(20)-trans-dien-3-one 3-α-acetyloxy-5-α-pregn-17(20)-cis-en-16-one 3-α-acetyloxy-5-α-pregnan-16-one 20S-acetyloxy-4-pregnene-3,16-dione

C25 H38 O6 C23 H36 O5 C21 H34 O4

CDCl3 CDCl3 CDCl3

[3] [3] [3]

C21 H30 O5 S C21 H30 O5 S C21 H32 O6 S C21 H28 O4 C21 H26 O4 C21 H26 O5 C23 H34 O3 C23 H34 O3 C21 H32 O 1 C23 H34 O4 ○ 1 C25 H36 O5 ○ C25 H36 O5 C27 H38 O7

CD3 OD CD3 OD CD3 OD CDCl3 CDCl3 CDCl3 CDCl3 CDCl3 CDCl3 CDCl3 CDCl3 CDCl3 CDCl3

[4] [4] [4] [5] [5] [5] [6] [6] [6] [6] [6] [6] [6]

C21 H32 O2 C22 H36 O3 C22 H34 O4 C23 H32 O3 C23 H34 O3 C23 H36 O3 C23 H32 O4

CDCl3 CDCl3 CDCl3 CDCl3 CDCl3 CDCl3 CDCl3

[7] [8] [8] [9] [9] [9] [9]

13-1-6 13-1-7 13-1-8 13-1-9 13-1-10 13-1-11 13-1-12 13-1-13 13-1-14 13-1-15 13-1-16 13-1-17 13-1-18 13-1-19 13-1-20 13-1-21 13-1-22 13-1-23 13-1-24 13-1-25 1 ○

The molecular formula in the main body was uncorrect, while that in the experimental section was right.

13.1 Common steroids |

3

Table 13-1-4: 1 H NMR spectroscopic data of pregnane-type steroids 13-1-3∼13-1-7. H

13-1-3

13-1-4

13-1-5

13-1-6

13-1-7

1

0.94 ddd (13.8, 7.8, 3.6)

0.92 ddd (12.0, 8.0, 3.6)

0.90 ddd (12.8, 7.6, 3.6)

0.92 ddd (13.8, 6.0, 5.4)

0.86 ddd (12.0, 6.0, 4.8)

0.93 ddd (12.8, 5.6, 4.0)

2

1.62 dm(7.8)

1.62 dm(8.0)

1.62 dm(7.6)

3

1.20 dddd (7.8, 4.8, 4.2, 3.6)

1.11 ddt (8.0, 4.8, 4.0)

1.08 ddt (8.0, 4.8, 4.0)

4

0.59 t(4.8) 0.64 dd(7.8, 4.8)

0.44 dd(8.0, 4.8) 0.65 t(4.8)

0.46 dd(8.0, 4.8) 0.64 t(4.8)

1.97 br ddd (13.6, 3.7, 3.6) 1.13 ddd (13.6, 13.5, 3.7) 2.08 dddd (13.0, 3.7, 3.6, 2.6) 1.67 dddd (13.5, 13.0, 11.6, 3.6) 4.16 dddd/tt (11.6, 11.6, 4.8, 4.8) 2.56 ddd (13.3, 4.8, 2.6) 2.36 ddddd (13.3, 11.6, 2.8, 2.5, 2.1)

1.90 br dddd (13.6, 3.7, 3.6,