The Alkaloids: Chemistry and Pharmacology 31

407 Pages·1987·14.02 MB·English

by  Arnold Brossi (Eds.)

THE ALKALOIDS
Chemistry and Pharmacology
Volume 31
THE ALKALOIDS
Chemistry and Pharmacology
A list of contents of volumes in this treatise is available from the publisher on request
THE ALKALOIDS
Chemistry and Pharmacology
Edited by
Arnold Brossi
National Institutes of Health
Bethesda, Maryland
VOLUME 31
ACADEMIC PRESS, INC.
Harcourt Brace Jovanovich, Publishers
San Diego New York Berkeley Boston
London Sydney Tokyo Toronto
COPYRIGHT 0 1987 BY ACADEMICPR ESS, INC.
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.
1250 Sixth Avenue, San Diego. California 92101
United Kingdom Edition published by
ACADEMIC PRESS INC. (LONDON) LTD.
24-28 Oval Road, London NWI 7DX
LIBRAROYF CONGRESCSA TALOCGA RDN UMBER: 50-5522
ISBN 0-12-469531-0 (alk. paper)
PRINTED IN THE UNITED STATES OF AMERICA
87 88 89 YO 9 8 7 6 5 4 3 2 I
CONTENTS
PREFACE. ......................................... .... ix
Chapter 1 . Reissert Synthesis of Isoquinoline and Indole Alkaloids
GABORB LASKO.P ETER KEREKESA. ND SANDORM AKLEIT
I . Introduction ....................................................... 1
I1 . Synthesis of Isoquinoline Alkaloids .................................... 5
111 . Synthesis of Indole Alkaloid Analogs ................................... 24
IV . Conclusion ........................................................ 21
References ........................................................ 27
Chapter 2 . Aristolochia Alkaloids
ZHONG-LIANGCH ENA ND DA-YUANZH U
I . Introduction ..... ............................................... 29
I1 . Structural Relations and Biosynthesis ............................... 30
I11 . Spectroscopic Properties ............................................. 36
IV . Chemical Reactions and Structural Determination ......................... 43
V . Chemical Synthesis .................. ................... 47
VI . Pharmacology and Clinical Use ....................................... 54
VII . Summary of Physical Properties ....................................... 62
References ........................................................ 62
Chapter 3 . Chromone Alkaloids
PETERJ . HOUGHTON
I . Introduction .......... 67
I1 . Botanical Distribution ............................................... 68
I11 . The Flavonoidal Alkaloids ............................................ 15
IV . Noreugenin-Related Alkaloids ......................................... 87
References ........................................................ 99
V
vi CONTENTS
Chapter 4 . Dibenzopyrrocoline Alkaloids
I . W . ELLIOTT
I . Introduction ....................................................... i01
I1 . History ....... 103
111 . Cryptaustoline and Cryptowoline ............. ............ 106
IV . Synthesis and Reactions of Dibenzopyrrocolines .......................... 108
V . Pharmacology . . ........................................ 114
References ................................... 115
Chapter 5 . Lupine Alkaloids
KH. A . ASLANOVY, u . K . KUSHMURADOAVN,D A . S . SADYKOV
I . Introduction ....................................................... 118
I1 . 13C-NMR Spectroscopy of Quinolizidine Alkaloids ....................... 132
111 . X-Ray Structural Investigation of Quinolizidine Alkaloids .................. 134
IV . Bicyclic Quinolizidine Alkaloids ....................................... 140
V . Tricyclic Quinolizidine Alkaloids ...................................... 146
VI . Tetracyclic Quinolizidine Alkaloids of the Sparteine Group ................. 155
VII . Tetracyclic Alkaloids of the Leontidine Group (Quinolizidine-Indolizidine
Alkaloids) ......................................................... 164
VIII . Tetracyclic Alkaloids of the Aloperine Group ............................ 167
IX . Tetracyclic Alkaloids of the Matrine Group .............................. 169
References .............................................. ... ....... 184
Chapter 6 . Alkaloids from Ants and Other Insects
ATSUSHIN UMATAA ND TOSHIROI BUKA
I . Introduction ............................................. ........ 194
I1 . Occurrence and Function ................................... ........ 194
111 . Structure and Synthesis .................................... ........ 238
References .............................................. .. ........ 302
Chapter 7 . Pavine and Isopavine Alkaloids
BELKISG OZLER
I . Introduction ............................................. ........ 317
I1 . Occurrence and Structure Elucidation ......................... ........ 319
111 . Synthesis ................................................ ........ 330
IV . Unnatural Pavines and Isopavines ............................ ........ 356
V . Spectral Properties ........................................ .. ........ 362
CONTENTS
VI. Biosynthesis ............................. ......................... 312
VII. Chemotaxonomic Considerations ............ ......................... 316
VIII. Homopavines and Homoisopavines ........... ......................... 378
IX. Aporphine-Pavine Dimers .................. ......................... 381
X. Pharmacology ............................ ......................... 383
References .............................. ......................... 384
INDEX ................................... ......................... 39 1
This Page Intentionally Left Blank
PREFACE
Discussion of the Reissert synthesis in connection with isoquinoline and indole
alkaloid synthesis follows a suggestion that important methods in alkaloid chem-
istry be reviewed. “Aristolochia Alkaloids” refers to a group of alkaloids casu-
ally discussed under “Aporphine Alkaloids,” now taken out of this context and
presented here for the first time as an independent group of alkaloids. Also for
the first time ‘‘Chromone Alkaloids” and ‘ ‘DibenzopyrrocolineA lkaloids” are
presented, many of them having interesting pharmacological properties, The
“Lupine Alkaloids” were discussed in Vols. 3, 7, and 9 of this treatise. This
classical group of alkaloids is updated here and presented by experts in the field.
“Alkaloids from Ants and Other Insects” presents compounds discussed earlier
under ‘ ‘Piperidine Alkaloids,’ ’ ‘‘Pyrrolizidine Alkaloids ,” “Simple Indo-
lizidine and Quinolizidine Alkaloids, ’ ’ and “Pyrrolidine Alkaloids, ’ ’ now con-
densed in one chapter summarizing these interesting natural products. “Pavine
and Isopavine Alkaloids, discussed under the heading ‘‘Isoquinoline Al-
”
kaloids” in Vols. 12 and 17 of this treatise, now comprises more than two dozen
alkaloids, justifying their presentation as a separate group of isoquinoline al-
kaloids. Occurrence, spectral properties, structures, and synthesis and bio-
synthesis are professionally covered, and pharmacological properties included
whenever known.
Arnold Brossi
ix