¹H NMR Handbook of Natural Products: Volume 6 Steroids, Tropolones, Cerebrosides, Marine Natural Products, Amino Acids, and Sugars 9783110631616, 9783110630817

Table of contents :
Contents
List of Participants
13 Steroids
14 Tropolones and cerebrosides
15 Marine natural products
16 Amino acids and sugars
Index of compound names
Index of molecular formula of compounds

Citation preview

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,