The Alkaloids: Chemistry and Pharmacology 22

361 Pages·1984·12.47 MB·English

by  Arnold Brossi (Eds.)

THE ALKALOIDS
Chemistry and Pharmacology
Volume XXII
This Page Intentionally Left Blank
THE ALKALOIDS
Chemistry and Pharmacology
Edited by
Arnold Brossi
Nutioncil lnstirurrs of Hecilth
Bethesdu. Morvland
Founding Editor
R. H. E Manske
VOLUME XXII
I983
ACADEMIC PRESS
A Subsidiary of Harcourt Brace Jovanovich, Publishers
New York 0 London
Paris 0 San Diego 0 San Francisco 0 Sao Paulo 0 Sydney 0 Tokyo 0 Toronto
COPYRIGH@T 1 983, BY ACADEMIPCR ESSI,N C.
ALL RIGHTS RESERVED.
NO PART OF THIS PUBLICATION MAY BE REPRODUCED OR
TRANSMITTED IN ANY FORM OR BY ANY MEANS, ELECTRONIC
OR MECHANICAL, INCLUDING PHOTOCOPY, RECORDING, OR ANY
INFORMATION STORAGE AND RETRIEVAL SYSTEM, WITHOUT
PERMISSION IN WRITING FROM THE PUBLISHER.
ACADEMIC PRESS, INC.
111 Fifth Avenue, New York. New York 10003
United Kimdoni Editiori ~irb/ishebdv
ACADEM~C PRESS, INC. (LONDON) LTD.
24/28 Oval Road, London NWl 7DX
LIBRAROYF CONGRESS CATALOG CARD NUMBER: 50 - 5 5 22
ISBN 0-12-469522-1
PRINTED IN THE UNITED STATES OF AMERICA
83848586 9 8 7 6 5 4 3 2 1
CONTENTS
LISTO F CONTRIBUTOR.S. . . . . . . . . . . . . . . . . . . . . . . . . vii
PREFACE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
CONTENTOSF PREVIOUVSO LUMES. . . . . . . . . . . . . . . . . . . . . . xi
Chapter 1. Ipecac Alkaloids and P-Carboline Congeners
Tozo Fum AND MASASHOI HBA
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . I
11. Occurrence . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
111. Chemistry and Synthesis . . . . . . . . . . . . . . . . . . . . . . . 5
IV. Related Compounds . . . . . . . . . . . . . . . . . . . . . . . . 22
V. Analytical Methods . . . . . . . . . . . . . . . . . . . . . . . . . 25
VI. Biosynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
VII. Biological Activity . . . . . . . . . . . . . . . . . . . . . . . . . 3 I
Addendum.. . . . . . . . . . . . . . . . . . . . . . . . . . . 32
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
Chapter 2. Elucidation of Structural Formula, Configuration, and Conformation of
Alkaloids by X-Ray Diffraction
ISABELLLA. KARLE
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
11. X-Ray Diffraction of Single Crystals . . . . . . . . . . . . . . . . . . 53
111. Alkaloids from Neotropical Poison Frogs . . . . . . . . . . . . . . . . 63
IV. Weberine and Polymethoxylated Analogs . . . . . . . . . . . . . . . . 71
V. Morphine, Agonists, and Antagonists . . . . . . . . . . . . . . . . . 74
VI. Selected Bisindole and Bisditerpene Alkaloids . . . . . . . . . . . . . . 76
VII. Veratridine, A Sodium Channel Neurotoxin . . . . . . . . . . . . . . . 79
VIII. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
References . . . . . . . . . . . . . . 81
V
vi CONTENTS
Chapter 3 . Putrescine. Spermidine. Spermine. and Related Polyamine Alkaloids
ARMING UGGISBERAGN D MANFREDHE SSE
I . Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
I1 . Occurrence of Natural Diamines and Polyamines . . . . . . . . . . . . . 85
111 . Structure Elucidation and Synthesis of Polyamine Alkaloids . . . . . . . . . 86
IV . Aspects of Biosynthesis and Chemotaxonomy of Polyamine Alkaloids . . . . . 146
V . Catalog of Naturally Occurring Diamine and Polyamine Alkaloids . . . . . . 150
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
Chapter 4 . Application of Enamide Cyclizations in Alkaloid Synthesis
ICHIYAN INOM~YANAD TAKEAKNIA ITO
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
I1 . Photocyclization of Enamides . . . . . . . . . . . . . . . . . . . . . 192
I11 . Thermal Cyclization of Enamides . . . . . . . . . . . . . . . . . . . 205
IV . Alkaloid Syntheses by the Application of Enamide Cyclization . . . . . . . . 210
V . Alkaloid Syntheses: Cyclization of Related Systems . . . . . . . . . . . . 251
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
Chapter 5 . The lmidazole Alkaloids
L . MAATA ND H . C . BEYERMAN
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
I1 . Bases Related to Histidine . . . . . . . . . . . . . . . . . . . . . . 282
111 . Pilocarpine: A Jaborandi Alkaloid . . . . . . . . . . . . . . . . . . 284
IV . Alkaloids Related to Pilocarpine . . . . . . . . . . . . . . . . . . . . 297
V . Other Imidazole Alkaloids . . . . . . . . . . . . . . . . . . . . . . 302
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
INDEX . . . . . . . . . . . . . . . . . . . . . 335
LIST OF CONTRIBUTORS
Numbers in parentheses indicate the pages on which the authors‘ contributions begin
H. C. BEYERMA(N2 81), Laboratory of Organic Chemistry, Delft University of
Technology, 2628 BL Delft, The Netherlands
TOZO FUJII( I), Faculty of Pharmaceutical Sciences, Kanazawa University.
Kanazawa 920, Japan
ARMING UGGISBER(8G5 ), Organisch-chemisches Institut der Universitat Zurich,
CH-8057 Zurich, Switzerland
MANFREDH ESSE (85), Organisch-chemisches lnstitut der Universitat Zurich,
CH-8057 Zurich, Switzerland
ISABELLA L. KARLE( 51), Laboratory for the Structure of Matter, Naval Re-
search Laboratory, Washington, D.C. 20375
L. MAAT (281), Laboratory of Organic Chemistry, Delft University of Technol-
ogy, 2628 BL Delft, The Netherlands
TAKEAKNIA ITO (l89), Kobe Women’s College of Pharmacy, Kobe, Japan
ICHIYA NINOMIYA( 189). Kobe Women’s College of Pharmacy, Kobe, Japan
MASASHOI HBAI() , Faculty of Pharmaceutical Sciences, Kanazawa University,
Kanazawa 920, Japan
This Page Intentionally Left Blank
PREFACE
Sophisticated physical techniques have had a major impact on alkaloid re-
search, particularly on the determination of novel structures. Progress in this area
will be reviewed periodically, and the chapter on “Elucidation of Structural
Formula, Configuration, and Conformation of Alkaloids by X-Ray Diffraction”
is the first of a series of such reviews. Attention is given to chemical methodol-
ogy, found to be most valuable in alkaloid synthesis, presented here in the
chapter on “Application of Enamide Photocyclization in Alkaloid Synthesis.”
Of a more traditional nature is the presentation of alkaloid classes, which have
not been reviewed for many years and where considerable new material has
accumulated. Hence, two chapters, namely, “The Imidazole Alkaloids,” last
reviewed in Vol. 111 (1953) and “Ipecac Alkaloids and P-Carboline Congeners,”
reviewed in Vol. XI11 (1971), are included.
An interesting group of alkaloid substances, not previously discussed in these
volumes, are the polyamine alkaloids; they are reviewed in a chapter entitled
“Putrescine, Spermidine, Spermine, and Related Polyamine Alkaloids.” Re-
cently available books on alkaloids of a general nature, primarily intended for
students of natural products, are not going to replace a treatise that continues to
be detailed, complete, and up-to-date.
Arnold Brossi
ix