The Alkaloids: Chemistry and Physiology 18

429 Pages·1981·19 MB·English

by  R.G.A. Rodrigo (Eds.)

THE ALKALOIDS
Chemistry and Physiology
Volume XVIII
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THE ALKALOIDS
Chemistry and Physiology
Foutzding Editor
R. H. F. MANSKE
Edited by
R. G. A. RODRIGO
Wilfrid Laurier University
Wrrrerloo, Ontario, Canudu
VOLUME XVIII
1981
ACADEMiC PRESS
NEW YORK 0 LONDON 0 TORONTO 0 SYDNEY 0 SAN FRANCISCO
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ACADEMIC PRESS, INC. (LONDON) LTD.
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Library of Congress Cataloging in Publication Data
Manske, Richard klrmth Fred, Date.
The alkaloids; chemistry and physioloqy.
Vols. 8-16 edited by R. H. F. Manske. vols. 17-
edited by R. H. F. Manske, R. G. A. Rogrigo.
Includes bibliographical references.
1. Alkaloids. 2. Alkaloids--Physiological effect.
I. tblmes, Henry Lavergne, joint author. 11. Title:
Thru physiology.
W421. M3 547.7'2 50-5522
ISBN 0-12-469518-3 (v. 18) AACRl
PRINTED IN THE UNITED STATES OF AMERICA
81 82 83 84 9 8 7 6 5 4 3 2 1
CONTENTS
LISTO F CONTRIBUTORS . . . . . . . . . . . . . . . . . . . . . . . . . . vii
PREFACE. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
CONTENTOSF PREVIOUVSO LUMES. . . . . . . . . . . . . . . . . . . . . xi
Chapter 1 . Erythrina and Related Alkaloids
S . F . DYKEA ND S . N . QUESSY
I . Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
I1 . Erythrina Alkaloids . . . . . . . . . . . . . . . . . . . . . . . . 2
111 . Homoerythrina Alkaloids . . . . . . . . . . . . . . . . . . . . . . 27
IV. Cephalotaxus Alkaloids . . . . . . . . . . . . . . . . . . . . . . 42
V. Biosynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
VI . Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
VII . Pharmacology . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
Chapter 2. The Chemistry of Cz,. Diterpenoid Alkaloids
S . WILLIAMPE LLETIAENRD NARESHV . MODY
I . Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
I1 . Veatchine-Type Alkaloids . . . . . . . . . . . . . . . . . . . . . 102
111 . Atisine-Type Alkaloids . . . . . . . . . . . . . . . . . . . . . . . 122
IV. Bisditerpenoid Alkaloids . . . . . . . . . . . . . . . . . . . . . . 144
V. Behavior and Formation of the Carbinolamine Ether Linkage in
Diterpenoid Alkaloids: The Baldwin Cyclization Rules . . . . . . . . . 149
VI . W-NMR Spectroscopy of CZrDiterpenoid Alkaloids . . . . . . . . . 160
VII . Mass Spectral Analysis of Czo-Diterpenoid Alkaloids . . . . . . . . . 163
VIII . Synthetic Studies . . . . . . . . . . . . . . . . . . . . . . . . . 168
IX . A Catalog of CZo-DiterpenoidA lkaloids . . . . . . . . . . . . . . . 1%
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
Chapter 3 . The 'T-NMR Spectra of Isoquinoline Alkaloids
D . W. HUGHESA ND D . B . MACLEAN
I . Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
I1 . 1,2,3,4 Tetrahydro and 3-4-Dihydroisoquinolines . . . . . . . . . . . 219
111 . Benzylisoquinoline Alkaloids . . . . . . . . . . . . . . . . . . . . 223
IV. Bisbenzylisoquinoline Alkaloids . . . . . . . . . . . . . . . . . . . 226
V. Cularine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
VI . The Morphine Alkaloids . . . . . . . . . . . . . . . . . . . . . . 228
V
vi CONTENTS
VII . Cancentrine Alkaloids . . . . . . . . . . . . . . . . . . . . . . . 230
VIII . Pavine Alkaloids . . . . . . . . . . . . . . . . . . . . . . . . . 234
IX . Aporphine Alkaloids . . . . . . . . . . . . . . . . . . . . . . . . 235
.
X Reduced and Nonreduced Proaporphines . . . . . . . . . . . . . . . 238
XI . Tetrahydroprotoberberine Alkaloids . . . . . . . . . . . . . . . . . 239
XI1 . Protopine Alkaloids . . . . . . . . . . . . . . . . . . . . . . . . . 243
XIII . Phthalideisoquinoline Alkaloids . . . . . . . . . . . . . . . . . . . 245
XIV. Modified Phthalideisoquinoline Alkaloids . . . . . . . . . . . . . . . 249
XV . Benzo[c]phenanthridie Alkaloids . . . . . . . . . . . . . . . . . . 250
XVI . Spirobenzylisoquinoline Alkaloids . . . . . . . . . . . . . . . . . . 252
XVII . Rhoeadine . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
XVIII . Secoberbine Alkaloids . . . . . . . . . . . . . . . . . . . . . . . 257
XIX . Emetine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
XX . Miscellaneous Alkaloids . . . . . . . . . . . . . . . . . . . . . . 260
References . . . . . . . . . . . . . . . . . . . . 261
Chapter 4 . The Lythraceae Alkaloids
W. MAREKG CKFBIEWSKANI D JERZY T . WROBEL
I . Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
I1 . Lactonic Biphenyl Alkaloids . . . . . . . . . . . . . . . . . . . . 266
Ill . Lactonic Biphenyl Ether Alkaloids . . . . . . . . . . . . . . . . . 281
IV. Simple Quinolizidine Alkaloids . . . . . . . . . . . . . . . . . . . 284
V. Ester Alkaloids . . . . . . . . . . . . . . . . . . . . . . . . . . 286
VI . Piperidine Metacyclophane Alkaloids . . . . . . . . . . . . . . . . 288
VII . Quinolizidine Metacyclophane Alkaloids . . . . . . . . . . . . . . . 294
VIII . Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
IX . Biosynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
X . Physiological Activity . . . . . . . . . . . . . . . . . . . . . . . 319
References . 3 20
Chapter 5 . Microbial and in Vitro Enzymic Transformations of Alkaloids
H . L . HOLLAND
I . Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
I1 . Enzymes Involved in Alkaloid Transformations . . . . . . . . . . . . 325
111 . Transformations of Indole Alkaloids . . . . . . . . . . . . . . . . . 328
IV. Transformations of Isoquinoline Alkaloids . . . . . . . . . . . . . . . 348
V. Transformations of Pyridine Alkaloids . . . . . . . . . . . . . . . . . 376
VI . Transformations of Pyrrolizidine Alkaloids . . . . . . . . . . . . . . 376
VII . Transformations of Quinoline Alkaloids . . . . . . . . . . . . . . . . 381
VIII . Transformations of Steroidal Alkaloids . . . . . . . . . . . . . . . . 383
IX . Transformations of Tropane Alkaloids . . . . . . . . . . . . . . . . . 391
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
INDEX. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
LIST OF CONTRIBUTORS
Numbers in parentheses indicate the pages on which the authors' contributions begin.
S. F. DYKE"( l), School of Chemistry, The University of Bath, Bath BA2
7AY, England
W. MAREKG OK~BIEW(S2K63I) , Department of Chemistry, University of
Warsaw, Warsaw 02-093, Poland
H. L. HOLLAND(32 31, Department of Chemistry, Brock University, St.
Catharines, Ontario L2S 3A 1, Canada
D. W. HUGHES(2 17), Department of Chemistry, McMaster University,
Hamilton, Ontario LSS 4M1, Canada
D. B. MACLEAN(2 17), Department of Chemistry, McMaster University,
Hamilton, Ontario L8S 4M1, Canada
NARESHV . MODY( 99), Institute for Natural Products Research, Depart-
ment of Chemistry, University of Georgia, Athens, Georgia 30602
S. WILLIAMP ELLETIE(R9 9), Institute for Natural Products Research,
Department of Chemistry, University of Georgia, Athens, Georgia
30602
S. N. QUESSY(l~) , School of Chemistry, The University of Bath, Bath
BA2 7AY, England
JERZYT . WROBEL(2 63), Department of Chemistry, University of Warsaw,
Warsaw 02-093, Poland
* Present address: Department of Chemistry, Queensland Institute of Technology, Bris-
bane, Queensland, Australia.
f Present address: Research and Development Department, Riker Laboratories,
Thornleigh, New South Wales, Australia.
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PREFACE
This volume of “The Alkaloids” presents timely reviews of three
groups, the Erythrim, Lythraceae, and C,,-diterpenoid alkaloids. The
chapters are organized in the traditional manner and cover all aspects of
the recent chemistry of these groups. A useful catalogue of Czo-
diterpenoid alkaloids is also included. One chapter is devoted to a discus-
sion of the I3Carbon spectra of benzylisoquinolines and the fifth chapter
collects and reviews work on the microbial and it? cirro transformations of
the alkaloids. Both subjects have attracted increasing attention in recent
years.
The editor wishes to thank the authors for their cooperation in making
this volume possible. We hope that it will be as useful to researchers in
alkaloid chemistry as the previous seventeen have been and we welcome
advice or criticism from our readers.
R. G. A. RODRICO
ix