The Alkaloids : Chemistry and Physiology

245 Pages·1982·8.821 MB·English

by  Arnold Brosse

THE ALKALOIDS
Chemistry and Physiology
Volume XIX
This Page Intentionally Left Blank
THE ALKALOIDS
Chemistry and Physiology
Founding Editor
R. H. F. Manske
Edited by
R.G.A.Rodrigo
Department of Chemistry
Wirfrid Lourier University
Waterloo, Ontario, Canada

VOLUME XIX
198 1
ACADEMIC PRESS
NEW YORK 0 LONDON TORONTO 0 SYDNEY 0 SAN FRANCISCO
A Subsidiary of Harcourt Brace Jovanovich, Publishers
COPYRIGHT @ 1981, BY ACADEMIPCR ESS, INC.
ALL RIGHTS RESERVED.
NO PART OF THIS PUBLICATION MAY BE REPRODUCED OR
TRANSMI'ITED 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 Kingdom Edition published by
ACADEMIC PRESS, INC. (LON DON) LTD.
24/28 Oval Road, London NWl 7DX
Library of Congress Cataloging in Plrblicatim Data
Mmske, Richard Helmuth Fred, Date.
me alkaloids; chemistry and physiology.
Vols. 8-16 edited by R. H. F. Mmske; vols. 17-
edited by R. H. F. Mmske, R. G. A. Rodrigo.
1. Alkaloids. 2. Alkaloids--Physiological effect.
I. Holmes, Henry Lavergne, joint author. 11. Title.
PD421.M3 547.7'2 50-5522
ISBN 0-l2-469519-1 (V. 19) AKR1
PRINTED IN THE UNITED STATES OF AMERICA
81 82 83 84 9 8 7 6 5 4 3 2 1
LISTO F CONTRIBUTORS . . . . . . . . . . . . . . . . . . . . . . . . . . vii
PREFACE. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
CONTENTS OF PREVIOUS VOLUMES . . . . . . . . . . . . . . . . . . . . . xi
Chapter 1 . Sceletium Alkaloids
PETERW . JEFFS
I . Historical Background . . . . . . . . . . . . . . . . . . . . . . . . 1
I1 . The Ring Systems of Sceletium Alkaloids . . . . . . . . . . . . . . . 4
I11 . Isolation and General Methods of Structure Determination . . . . . . . . 5
IV. Structural Classes . . . . . . . . . . . . . . . . . . . . . . . . . . 6
V. Synthesis of Sceletium Alkaloids . . . . . . . . . . . . . . . . . . . 33
VI . Miscellaneous Chemical Transformations of Mesembrine Alkaloids . . . . 54
VII . Biosynthetic Studies . . . . . . . . . . . . . . . . . . . . . . . . . 60
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
Chapter 2 . Solanum Steroid Alkaloids
HELMUTR IPPERGEARN D KLAUS SCHREIBER

I . Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . a1
I1 . Occurrence of Glycoalkaloids and Alkamines . . . . . . . . . . . . . a5
111 . Glycoalkaloids . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
IV. The Alkamines . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
V. Biochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
VI . Tables of Physical Constants . . . . . . . . . . . . . . . . . . . . . 156
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1a3
Chapter 3 . Phenanthroindolizidine and Phenanthroquinolizidine Alkaloids
I . RALPHC . BICKA ND WANNEES INCHAI
I . Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
I1 . Structures and Configurations . . . . . . . . . . . . . . . . . . . . 193
111 . Occurrence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
IV. Degradative Experiments and Structural Determination . . . . . . . . . 197
V. Electronic Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . 198
VI . Infrared Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . 199
VII . Mass Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
VIII . Nuclear Magnetic Resonance Spectra . . . . . . . . . . . . . . . . . 2001
I X . Stereoc hemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
X . Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
V
vi CONTENTS
XI . Biosynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
XI1 . Biological Activity . . . . . . . . . . . . . . . . . . . . . . . . . 217
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
INDEX. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
LIST OF CONTRIBUTORS
Numbers in parentheses indicate the pages on which the authors’ contributions begin.
I. Ralph C. Bick (193), Chemistry Department, University of Tasmania,
Hobart, Australia
Peter W. Jeffs (l), Department of Chemistry, Paul M.G ross Laboratory,
Duke University, Durham, North Carolina 27706
Helmut Ripperger (81), Institute of Plant Biochemistry of the Academy of
Sciences of the GDR, DDR-402 Halle/Saale, German Democratic Re-
public
Klaus Schreiber (81), Institute of Plant Biochemistry of the Academy of
Sciences of the GDR, DDR-402 Halle/Saale, German Democratic Re-
public
Wannee Sinchai* ( 193), Chemistry Department, University of Tasmania,
Hobart, Australia

* Present address: Chemistry Department, Faculty of Science, Prince of Songkla Univer-
sity, Haadyai, Thailand.
vii
This Page Intentionally Left Blank
Advances in the chemistry of three groups of alkaloids are reviewed
in this volume. The Sceletium and Phenanthroindolizidine-Phenanthro-
quinolizidine groups were previously reviewed in Volume IX of this
series and a chapter on the Solunum alkaloids appeared in Volume X.
The present reports deal with the considerable research activity in these
areas over the intervening years.
The editor wishes to thank the authors for their cooperation and wel-
comes advice or criticism from our readers.
R. G. A. RODRIGO

ix