13C-NMR of Natural Products, Volume 2: Diterpenes

798 Pages·1992·60.089 MB·English

by  Atta-ur-Rahman, Viqar Uddin Ahmad

13C-NMR of
Natural Products
Volume 2
Diterpenes
13C-NMR of
Natural Products
Volume 2
Diterpenes
Atta-ur-Rahman
and
Viqar Uddin Ahmad
H.E.J. Research Institute of Chemistry
University of Karachi
Karachi, Pakistan
Springer Science+Business Media, LLC
Llbrary of Congress Cataloglng-ln-Publlcatlon Data
13C-NMR of natural products / Atta-ur-Rahman and Viqar Uddin
Ahmad.
p. cm.
Includes bibliographical references and index.
Contents: v. 1. Monoterpenes and sesquiterpenes v.
2. Dlterpenes.
ISBN 978-1-4613-6446-7 ISBN 978-1-4615-3288-0 (eBook)
DOI 10.1007/978-1-4615-3288-0
1. Nafural products--Analysis. 2. Nuclear magnetiC resonance
spectroscopy. 1. Rahman. Atta-ur-, 1942- II. Ahmad, Viqar Uddin.
III. Title: Carbon-thirteen NMR of natural products.
OD415.A267 1991
547.3·0877--dc20 91-10877
CIP
ISBN 978-1-4613-6446-7
© 1992 Springer Science+Business Media New York
Originally published by Plenum Press, New York in 1992
AlI rights reserved
No part of this book may be reproduced, stored in a retrievai system, or transmitted
in any form or by any means, electronic, mechanical, photocopying, microfilming,
recording, or otherwise, without written permis sion from the Publisher
PREFACE
Natural product chemistry presents a vast and exciting area which has attracted the attention of some of the
foremost organic chemists. With the development of modem spectroscopic techniques, the number of new natural
products continues to grow exponentially thereby placing at the hands of phytochemists and pharmacologists a vast array
of novel and interesting compounds with potential for drug development. The need for books which present spectral data
of such compounds has accordingly grown.
The present volume, which is the second of this new series, covers the J3C-NMR data of diterpenes reported till
late 1989. The compounds are arranged according to their structural types in various subclasses. Within each subclass,
they are arranged in order of increasing molecular weight Compounds in the same subclass and having the same
molecular weight are arranged in order to increasing carbon number while those having the same molecular formula are
arranged alphabetically. In case the J3C-chemical shifts were not assigned by the authors, then these are presented
unassigned below the structures. If the chemical shifts have been reported in several solvents, then the values presented
are those in CDC13, but references have been included to their data in other solvents. We have avoided giving long
chemical names of compounds and used trivial names but where trivial names were not given by the authors, then the
compounds have been designated by alphabets (representing the first alphabets of the plant genus and species) followed
by a number. The data given is for natural compounds and the data for simple derivatives has only been given where the
data of the parent natural compounds was not available. The symbols *,**, ***, +, ++, +++, #, @, $, ct., &, have been
employed to indicate interchangeability of assigned values.
The numbering systems used are given at the beginning of each subclass. Compound name, molecular formula,
molecular weight, source and compounds-type indices have been included, which should add to the utility of the book.
The authors wish to thank the following research fellows for their help in the literature survey: Miss Anis
Fatima, Miss Jahan Ara, Miss Nazli Rasool, Miss Rehana Perveen, Miss Rubeena Saleem, Miss Saleha Ishrat, Miss
Seema Iqbal, Miss Shahida Begum and Miss Zahida Begum. We are grateful to Mr. Kamran Faisal Khan, Mr.
Mohammad Afzal Butt, Mr. Wajih-ul-Hasnain, Mr, Mohammad Shakir and Mr. Asif Mehmood Raja for typing of the
manuscript. Our thanks go to Mr. Mehmood Alam for the secretarial work and to Mr. Abdul Hafeez for drawing the
structures. We are indebted to Zelin Private Limited (Karachi), Pakistan Atomic Energy Commission (Islamabad),
Sumitomo Corporation (Tokyo) and Rotary Club (Karachi) for financial support.
Finally we wish to express our sincere gratitude to Prof. K. Antonakis, Prof. F. Arcamone, Prof. Y. Asakawa,
Dr. Fatima Z. Basha, Prof. Jan Bergman, Prof. H.1. Bestmann, Prof. H. Budzikiewicz, Prof. L. Castedo, Prof. M.
Chierichetti, Prof. J.D. Connolly, Prof. B. Danieli, Prof. S. Dev, Prof. H. Duddeck, Mr. E.B. Gapit, Prof. B.Q. Guevara,
Prof. T. Higa, Dr. H. Hirota, Miss J. Hudson, Dr. Byung-Hoon Han, Prof. S. Ito, Prof. P. Joseph-Nathan, Prof. J. Jurczak,
Dr. L. Kenne, Prof. S.V. Kessar, Prof. W. Kraus, Prof. J.P. Kutney, Dr. J. McLeod, Prof. P.w. Le Quesne, Prof. J. Levy,
Mr. K. Mahmood, Dr. S. Malik, Prof. K. Mori, Dr. T. Nakano, Prof. Nanjun-Sun, Prof. I. Ninomiya, Prof. M. Nishizawa,
Prof. C. Oehlschlager, Prof. K.A. Parker, Dr. A. Panthong, Prof. J.H. Pazur, Prof. G.D. Prestwich, Prof. A.V. Rama Rao,
Prof. V. Reutrakul, Prof. M.Y. Sargent, Prof. P. Sinay, Prof. Y. Shizuri, Prof. G. Snatzke, Prof. W. Steglich, Prof. c.
Szantay, Dr. F. Tillequin, Prof. A. Vasella, Prof. R. Verpoorte, Prof. R. Vlahov, Prof. W. Voelter, Prof. D. Walton, Prof.
Z.J. Witczak. Prof. Xu.xing-Xiang, Prof. X.x. Xu, Prof. Yong-Long Liu, Prof. A. Zamojski and Prof. K.P. Zeller for
supply of copies of various publications.
Atta-ur-Rahman
Ph.D. (Cantab.), Sc.D. (Cantab).
Viqar Uddin Ahmad
Ph.D. (Kar.), Dr.rer.nat. (Bonn)
v
CONTENTS
Diterpenes
Linear ............................................................................. 3
Difuran Terpenoid .................................................................... 23
Oxepane ................................. , .... " .......... , ........................ 26
Bisabolane Isoprenologue ............................................................... 28
Retinane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 30
Labdane ........................................................................... 33
Seco-Labdane ...................................................................... 136
Chettaphanane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 139
Seco-Chettaphanane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 144
Clerodane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 146
Pimarane ......................................................................... 248
Abietane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 286
Seco-Abietane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 318
Abeo-Abietane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 320
Totarane 324
Kaurane 325
Seco-Kaurane ...................................................................... 380
Beyrane .......................................................................... 383
Seco-Beyrane ...................................................................... 391
Cassane .......................................................................... 392
Seco-Cassane ...................................................................... 394
Cleistanthane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 395
Seco-Cleistanthane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . " 399
Rosane .................................................................... '" .. " 400
Lanugon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 407
Coleon ........................................................................... 410
VII
Spongian .................................•....................................... 412
Seco-Spongian . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 430
Gibbane .......................................................................... 435
Trachylobane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 436
Atisane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 438
Cembrane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 446
Seco-Cembrane ..................................................................... 479
Iso-Cembrane ...................................................................... 480
Casbane .......................................................................... 482
Berdimerane 484
Dollabellane 486
Dolastane ......................................................................... 504
Grindelane ........................................................................ 511
Ericacane ......................................................................... 513
Fusicoccin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 514
Seco-Fusicoccin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 516
Ja trophane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 517
Xeniaphyllane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 519
Xenicin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 525
Guiane Isoprenologue . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 535
Portulal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 541
Undecane 544
Daphnane 547
Tigliane 549
•••••••••••••••••••• Ii •••••••••••••••••••••••••••••••••••••••••••••••••••••
Briarane 552
Cladiellane ........................................................................ 566
Asbestinin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 572
Cubitane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 575
VIII
Cyclonane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 578
Biflorane ......................................................................... 584
Germacrane Isoprenologue ............................................................. 594
Sacculatane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 598
Irieol ............................................................................ 599
Spatane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 603
Ginkgolide ........................................................................ 605
Crotofolane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 608
Stemodane ........................................................................ 609
Enmein ........................................................................... 611
Verrucosane 614
Barbacenane 615
Trinerverane 617
Viscidane ......................................................................... 619
Miscellaneous Diterpenes 622
Indexes
Name Index ....................................................................... 681
Source Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 699
Compound Type Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 725
Molecular Formula Index .............................................................. 745
Molecular Weight Index ............................................................... 775
IX
DITERPENES
LINEAR
Basic skeleton:
20 16
111111111111!llllllllllllllllllllllllllllllllil!111111IIIIIIIIIIIIIIIII!IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII!IIIIIIII
B-SPRINGENE
Source: Antidorcas marsupiaZis
Mol. formula: C20H32
Mol. wt.: 272
Solvent: CDCl3
17.7 16.0 16.0
B.V. Burger, M. Le Roux. H.S.C. Spies. V. Truter and R.C. Bigalke. Tetrahedron
Lett., (52), 5221 (1978).
3
(5~. 9~)-13.14-EPOXY-6.10.14-TRIMETHYLPENT ADECA-5. 9-DIEN-2-0NE
Source: Cystophol'a monilifo1'l11is
Mol. formula: C18H3002
Mol. wt.: 278
Solvent: CDCl3
o
CH : 15.8, 15.8, 18.6, 27.3 and 29.8
3
CH2: 22.3, 24.8, 26.3, 36.2, 39.5 and 43.6
CH: 64.1, 122.7 and 124.7
C: 58.2, 134.2 and 136.3
C=O: 208.8
•
LA. van Altena, Aust. J. Chern., 41 (1), 49 (1988).
1I1111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111III
(2E,6E.10E.13E)-3, 7, 1l,15-TETRAMETHYL-HEXADECA-2,6, 10,
- - - - 13,15-PENTENOL
Source: Biful'caria biful'cata
Mol. formula: C20H 320
Mol. wt.: 288
Solvent: CDCl3
42.7 125.1 39.4 123.8 39.4 123.4
18.5
OH
114.3 15.9 15.8 16.1
L. Semmak, A. Zerzouf, R. Valls, B. Banaigs, G. Jeanty and C. Francisco, Phyto
chemistry, 27(7), 2347 (1988).
4