¹H NMR Handbook of Natural Products: Volume 4 Monoterpenoids and Sesquiterpenoids 9783110631593, 9783110630787

Table of contents :
Contents
List of Participants
8 Monoterpenoids
9 Sesquiterpenoids
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

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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 Volume 6: Steroids, Tropolones, Cerebrosides, Marine Natural Products, Amino Acids, and Sugars Hailin Qin, Dequan Yu, 2021 ISBN 978-3-11-063081-7, e-ISBN (PDF) 978-3-11-063161-6, e-ISBN (EPUB) 978-3-11-063092-3

Hailin Qin, Dequan Yu

1

H NMR Handbook of Natural Products |

Volume 4: Monoterpenoids and Sesquiterpenoids

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 978-3-11-063078-7 e-ISBN (PDF) 978-3-11-063159-3 e-ISBN (EPUB) 978-3-11-063102-9 Library of Congress Control Number: 2021931821 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: Michel VIARD / iStock / Getty Images Plus Typesetting: VTeX UAB, Lithuania Printing and binding: CPI books GmbH, Leck www.degruyter.com

Contents List of Participants | VII 8 8.1 8.2 8.3 8.4 8.5 8.5.1 8.5.2 8.5.3 8.5.4 8.5.5 8.5.6 8.5.7

Monoterpenoids | 1 Acyclic monoterpenoids | 1 Monocyclic monoterpenoids | 14 Dicyclic monoterpenoids | 36 Tricyclic monoterpenoids | 37 Iridoids | 43 Normal iridoids | 43 Dimeric iridoids | 82 Trimeric and tetrameric iridoids | 94 Secoiridoids | 99 Secoiridoids containing lactone ring in molecular structure | 118 Iridoids containing extra carbons in molecular skeleton | 125 Noriridois | 126

9 9.1 9.2 9.3 9.4

Sesquiterpenoids | 137 Farnesane-type sesquiterpenoids | 137 Monocyclofarnesane-type sesquiterpenoids | 142 Bicyclofarnesane-type sesquiterpenoids | 147 Bisabolane-, majapolane-, and heliannane-type sesquiterpenoids | 152 Bergamotane-, campherenane-, isocampherenane-, and santalane-type sesquiterpenoids | 157 Cuparane-, cyclolaurane-, gymnomitrane-, herbertane-, laurane-, and trichothecane-type sesquiterpenoids | 163 Chamigrane- and widdrane-type sesquiterpenoids | 175 Acorane- (cedrane- or anislactone-), carotane-, and prezizaane-type sesquiterpenoids | 178 Cadinane-, copaane-, copacamphane-, cyclocopacamphane-, cubebane-, oplopane-, and picrotoxane-type sesquiterpenoids | 185 Himachalane- and longipinane-type sesquiterpenoids | 200 Botryane-, caryophyllane-, fascicularone-, modhephene-, silphinane-, subergane-, and suberosane-type sesquiterpenoids | 204 Africanane-, capnellane-, hirsutane-, humulane-, illudalane-, illudane-, proilludane-, and tremulane-type sesquiterpenoids | 219 Germacrane-type sesquiterpenoids | 234 Elemane-type sesquiterpenoids | 250 Eudesmane-, lindenane-, and oppositane-type sesquiterpenoids | 253

9.5 9.6 9.7 9.8 9.9 9.10 9.11 9.12 9.13 9.14 9.15

VI | Contents 9.16 9.17 9.18 9.19

9.20 9.21 9.22 9.23

Spiroaxane- and vetisperane-type sesquiterpenoids | 265 Eremophilane- and bakkane-type sesquiterpenoids | 269 Guaiane-, pseudoguaiane-, bourbonane-, xanthane-, patchoulane-, and carabrane-type sesquiterpenoids | 277 Aromadendrane-, bicyclogermacrane-, aristolane-, nardosinane-, valerenane-, gorgonane-, brasilane-, and pacifigorgiane-type sesquiterpenoids | 293 Pinguisane-type sesquiterpenoids | 306 Cyclomyltaylane-type sesquiterpenoids | 308 Salviolane-type sesquiterpenoids | 310 Some additional sesquiterpenoids | 312

Index of compound names | 335 Index of molecular formula of compounds | 353

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

8 Monoterpenoids 8.1 Acyclic monoterpenoids

Table 8-1-1: Compounds, MFs, and test solvents of acyclic monoterpenoids 8-1-1∼8-1-48. No.

Compounds

MFs

Test solvents

References

8-1-1 8-1-2 8-1-3 1 8-1-4○ ○ 8-1-5 2 8-1-6 8-1-7 8-1-8 8-1-9 8-1-10 8-1-11 8-1-12 8-1-13

7-hydroperoxy-5,6-E-dehydro-6,7-dihydronerol 3,7-dimethyloct-1-en-6-one 3,7-dimethyl-5-hydroxyoct-1-en-6-one 6(S)-hydroxy-2,6-dimethyl-2(E)-7-octadienoic acid (+)-1-hydroxylinalool 6-oxo-8-hydroxy-santolina-1,4-diene 5,8-epoxy-4,6-dihydroxy-santolin-1-ene sachalinol A (3S,6S)-6,7-dihydroxy-6,7-dihydrolinalool (3S,6R)-6,7-dihydroxy-6,7-dihydrolinalool (2E,4E)-3,7-dimethyl-2,4-octadiene deoxygeraniol trans-5-hydroxy-2-isopropenyl-5-methylhex-3-en1-ol 4-hydroxy-2-isopropenyl-5-methylene-hexan-1-ol rhodioloside E rhodioloside D rhodioloside C rhodioloside B rhodioloside F rhodioloside A (3S)-O-α-L-rhamnopyranosyl-(1→3)-[4-O-(E)coumaroyl]-α-L-rhamnopyranosyl-(1→6)-β-Dglucopyranosyl-linalool (3S)-O-α-L-rhamnopyranosyl-(1→3)-[4-O-(Z)coumaroyl]-α-L-rhamnopyranosyl-(1→6)-β-Dglucopyranosyl-linalool (3S)-3-O-(3󸀠 ,4󸀠 -diangeloyl-β-Dglucopyranosyloxy)-7-hydroperoxy-3,7dimethylocta-1,5-diene (3S)-3-O-(3󸀠 ,4󸀠 -diangeloyl-β-Dglucopyranosyloxy)-6-hydroperoxy-3,7dimethylocta-1,7-diene (3S)-8-hydroxy-6,7-dihydrolinallol 3-O-β-D-glucopyranoside (3S,6E)-8-hydroxylinalool 3-O-β-D-(3-O-potassium sulfo)glucopyranoside

C10 H18 O3 C10 H18 O C10 H18 O2 C10 H16 O3 C10 H18 O2 C10 H16 O2 C10 H18 O3 C10 H20 O3 C10 H20 O3 C10 H20 O3 C10 H18 C10 H18 C10 H18 O2

CDCl3 CDCl3 CDCl3 CDCl3 CDCl3 CDCl3 CDCl3 CD3 OD C5 D5 N C5 D5 N CDCl3 CDCl3 –

[1] [2] [2] [3] [3] [4] [4] [5] [6] [6] [7] [8] [9]

C10 H18 O2 C21 H38 O11 C16 H30 O8 C22 H38 O12 C22 H38 O12 C21 H36 O11 C16 H28 O8 C37 H54 O16

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

[10] [11] [11] [11] [11] [12] [11] [13]

C37 H54 O16

CD3 OD

[13]

C26 H40 O10

CDCl3

[14]

C26 H40 O10

CDCl3

[14]

C16 H30 O7

C5 D5 N

[6]

C16 H27 KO10 S

C5 D5 N

[6]

8-1-14 8-1-15 8-1-16 8-1-17 8-1-18 8-1-19 8-1-20 8-1-21 8-1-22 8-1-23 8-1-24 8-1-25 8-1-26

https://doi.org/10.1515/9783110631593-008

2 | 8 Monoterpenoids Table 8-1-1 (continued) No.

Compounds

MFs

Test solvents

References

8-1-27

(3S,6S)-6,7-dihydroxy-6,7-dihydrolinalool 3-O-β-D-glucopyranoside (3S,6R)-6,7-dihydroxy-6,7-dihydrolinalool 3-O-β-D-glucopyranoside (3S,6R)-6,7-dihydroxy-6,7-dihydrolinalool-3-O-βD-(3-O-potassium sulfo)-glucopyranoside (2E,6Z)-2,6-dimethyl-8-β-D-glucosyloxy-2,6octadienoic acid (2E,6R)-2,6-dimethyl-8-hydroxy-2-octenoic acid 8-O-[6󸀠 -O-(E)-p-coumaroyl]-β-D-glucopyranoside kudingoside A kudingoside B portuloside A 3,7-dimethyl-2(E),6-octadien-5-one-1-O-β-Dglucoside 3,7-dimethyl-3(E),6-octadien-5-one-1-O-β-Dglucoside 2α-(3-methylbut-2-enyl)-3-methyl-2,53 dihydrofuran○ 2β-(3-methylbut-2-enyl)-3-methyl-2,53 dihydrofuran○ 2-hydroxy-2-(3-methylbut-2-enyl)-3-methyl-2,53 dihydrofuran○ vitexoid sachalinol B sachalinol C 1,10-oxy-β-myrcene hydroxide 1,10-oxy-α-myrcene hydroxide sachalinoside B dissectol A lappaceolide A lappaceolide B

C16 H30 O8

C5 D5 N

[6]

C16 H30 O8

C5 D5 N

[6]

C16 H29 KO11 S

C5 D5 N

[6]

C16 H26 O8

CD3 COCD3

[15]

C25 H34 O10

CD3 OD

[16]

C31 H44 O12 C31 H44 O13 C16 H26 O7 C16 H26 O7

CD3 OD CD3 OD C5 D5 N CD3 OD

[17] [17] [18] [19]

C16 H26 O7

CD3 OD

[19]

C10 H16 O

CDCl3

[20]

C10 H16 O

CDCl3

[20]

C10 H16 O2

CDCl3

[20]

C10 H16 O3 C10 H18 O3 C10 H18 O3 C10 H16 O2 C10 H16 O2 C16 H28 O7 C16 H26 O7 C10 H12 O6 C10 H12 O6

CDCl3 CD3 OD CD3 OD CDCl3 CDCl3 CD3 OD C5 D5 N CDCl3 CDCl3

[21] [5] [5] [10] [10] [5] [22] [23] [23]

8-1-28 8-1-29 8-1-30 8-1-31 8-1-32 8-1-33 8-1-34 8-1-35 8-1-36 8-1-37 8-1-38 8-1-39 8-1-40 8-1-41 8-1-42 8-1-43 8-1-44 8-1-45 8-1-46 8-1-47 8-1-48 1 ○

Product of hydrolysis. Product of reduction. 3 ○ Designation of original literature. 2 ○

8.1 Acyclic monoterpenoids | 3

4 | 8 Monoterpenoids

8.1 Acyclic monoterpenoids | 5

Table 8-1-2: 1 H NMR spectroscopic data of acyclic monoterpenoids 8-1-1∼8-1-5. H

8-1-1

8-1-2

8-1-3

1

4.59 dq(7.0, 1.0)

4.98 d(18)

5.05 d(18)

2

5.41 tqdd(7.0, 1.5,