Alkaloids: Chemical and Biological Perspectives

S. William Pelletier Editor

Alkaloids: ChelIlical and Biological Perspectives

Volume 8

Springer-Verlag New York Berlin Heidelberg London Paris Tokyo Hong Kong Barcelona Budapest

S. William Pelletier Institute for Natural Products Research

and The School of Chemical Sciences The University of Georgia Athens, Georgia 30602, USA

Volumes 1-6 of Alkaloids: Chemical and Biological Perspectives were published by John Wiley & Sons, New York, New York.

ISSN: 0735-8210 Printed on acid-free paper.

© 1992 Springer-Verlag New York Inc. Softcover reprint of the hardcover 1st edition 1992

All rights reserved. This work may not be translated or copied in whole or in part without the written permission of the publisher (Springer-Verlag New York, Inc., 175 Fifth Avenue, New York, NY 10010, USA), except for brief excerpts in connection with reviews or scholarly analysis. Use in connection with any form of information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed is forbidden. The use of general descriptive names, trade names, trademakes, etc., in this publication, even if the former are not especially identified, is not to be taken as a sign that such names, as understood by the Trade Marks and Merchandise Marks Act, may accordingly be used freely by anyone.

Production coordinated by Chernow Editorial, Inc. and managed by Christin R. Ciresi; manu­facturing supervised by Jacqui Ashri.

Typeset by Asco Trade Typesetting Ltd., Hong Kong.

9 8 7 6 5 4 3 2 1

ISBN -13 :978-1-4612-7715-6 e-ISBN -13 :978-1-4612-2908-7 DOl: 10.1007/978-1-4612-2908-7

Dedicated to Derek Harold Richard Barton

(1918- )

In 1953, Barton realized that on theoretical grounds the formula ofPummerer's ketone, and hence the biosynthesis of morphine according to Robinson, must be wrong. He then developed (with T. Cohen, 1957) a rational theory for the biosynthesis of all phenolic alkaloids. Work in the greenhouse eventually confirmed almost all the predictions starting with morphine [in association" with W. Steglich (1963) and partly with A.R. Battersby (1965)], alkaloids, sinomenine, Amaryllidaceae alkaloids, especially galantamine (G.W. Kirby, 1960-1963), proaporphine alkaloids like crotonosine (1963) and finally the Erythrina alkaloids (1966 and 1968) where the simplest phenolate radical coupling had to be replaced by a more complex one (1974). He was also the author of the first paper on conformation analysis (1950) which applies to all classes of molecules. In later life (1960-), he was mainly concerned with the discovery and invention of new chemical reactions for use in synthesis, including manipulation and synthesis of alkaloids.

Preface

Volume 8 of this series presents four timely reviews on alkaloids: Chapter 1 is a magnificent and monumental review of curare, "a group of dart and/or arrow poisons varying in composition and featuring muscle relaxation as their basic pharmacological action." The fascinating history of curare is recounted, beginning with early encounters by the Spanish Conquistadores through its use as arrow poisons by the forest tribes in hunting and warfare, its chemistry, ethnography, botany and pharmacology. A terminal section of this chapter treats the development of modern muscle relaxants. This chapter thus traces how curare-initially only a crude plant extract-has given rise to the widely used and very important neuromuscular blocking agents of today.

The precise role of plant secondary metabolites and their interactions with insect herbivores have been focal points for research by chemists, botanists and entomologists for many years. Alkaloids and their glycosides are frequently involved as feeding deterrents. Chapter 2 treats the relationships between the chemistry of alkaloids in host plants and the effects that these compounds may have on insect herbivores. Interestingly, an alkaloid produced by a plant may manifest different effects on different insects.

Members of the yohimbine family of alkaloids exhibit a wide range of medicinal properties. The diverse biological activity of these compounds and their intriguing structures have stimulated the interest of synthetic or­ganic chemists. Several of these complex alkaloids, such as reserpine and yohimbine, present challenging synthetic targets. Chapter 3 reviews de­velopments in the synthesis of yohimbine alkaloids over the past twelve years, focusing particularly on the approaches used to synthesize target molecules.

Chapter 4 summarizes available knowledge about the loline-type pyrrolizi­dine alkaloids. These alkaloids have been reported from only a few genera of grasses (Poaceae). Their occurrence in grasses is closely associated with the presence of endophytic fungi. The chapter treats isolation, characterization, synthesis and the biological activities of these alkaloids.

vii

viii Preface

Each chapter in this volume has been reviewed by at least one expert in the field. Indexes for both subjects and organisms are provided.

The editor invites prospective contributors to write him about topics for review in future volumes in this series.

s. William Pelletier Athens, Georgia August 1991

Contents

Preface vii

Contributors xi

Contents of Previous Volumes xiii

1. Curare 1 Norman G. Bisset

2. Alkaloid Chemistry and Feeding Specificity of Insect Herbivores 151 James A. Saunders, Nichole R. O'Neill, and John T. Romeo

3. Recent Advances in the Synthesis of Yohimbine Alkaloids 197 Ellen W. Baxter and Patrick S. Mariano

4. The Loline Group of Pyrrolizidine Alkaloids 320 Richard G. Powell and Rich(lrd J. Petroski

Subject Index 339

Organism Index 357

ix

Contributors

Ellen W. Baxter, The R.W. Johnson Pharmaceutical Research Institute, Welsh and McKean Roads, Spring House, PA 19477-0776, USA

Norman G. Bisset, Pharmacognosy Research Laboratories, Chelsea Depart­ment of Pharmacy, King's College London, University of London, Manresa Road, London SW3 6LX, England

Patrick S. Mariano, Department of Chemistry and Biochemistry, The Uni­versity of Maryland, College Park, MD 20742, USA

Nichole R. O'Neill, U.S. Department of Agriculture, Agricultural Research Service, Beltsville, MD 20705, USA

Richard J. Petroski, National Center for Agricultural Utilization Research, 1815 North University Street, Peoria, IL 61604, USA

Richard G. Powell, National Center for Agricultural Utilization Research, 1815 North University Street, Peoria, IL 61604, USA

John T. Romeo, Biology Department, University of South Florida, Tampa, FL 33620, USA

James A. Saunders, U.S. Department of Agriculture, Agricultural Research Service, Beltsville, MD 20705, USA

xi

Contents of Previous Volumes

Volume 1

1. The Nature and Definition of an Alkaloid S. William Pelletier

1

2. Arthropod Alkaloids: Distribution, Functions, and Chemistry 33 Tappey H. Jones and Murray S. Blum

3. Biosynthesis and Metabolism of the Tobacco Alkaloids 85 Edward Leete

4. The Toxicology and Pharmacology of Diterpenoid Alkaloids 153 M.H. Benn and John M. Jacyno

5. A Chemotaxonomic Investigation of the Plant Families of Apocynaceae, Loganiaceae, and Rubiaceae by Their Indole Alkaloid Content 211

M. Volkan Kisakiirek, Anthony J.M. Leeuwenberg, and Manfred Hesse

Volume 2

1. Some Uses of X-ray Diffraction in Alkaloid Chemistry 1 Janet Finer-Moore, Edward Arnold, and Jon Clardy

2. The Imidazole Alkaloids 49 Richard K. Hill

3. Quinolizidine Alkaloids of the Leguminosae: Structural Types, Analyses, Chemotaxonomy, and Biological Properties 105

A. Douglas Kinghorn and Manuel F. Balandrin

xiii

xiv Contents of Previous Volumes

4. Chemistry and Pharmacology of the Maytansinoid Alkaloids 149 Cecil R. Smith, Jr. and Richard G. Powell

5. 13C and Proton NMR Shift Assignments and Physical Constants of CwDiterpenoid Alkaloids 205

S. William Pelletier, Naresh V. Mody, Balawant S. Joshi, and Lee C. Schramm

Volume 3

1. The Pyridine and Piperidine Alkaloids: Chemistry and Pharmacology 1

Gabor B. Fodor and Brenda Colasanti

2. The Indolosesquiterpene Alkaloids of the Annonaceae 91 Peter G. Waterman

3. Cyclopeptide Alkaloids 113 Madeleine M. Joullie and Ruth F. Nutt

4. Cannabis Alkaloids 169 Mahmoud A. EISohly

5. Synthesis of Lycopodium Alkaloids 185 Todd A. Blumenkopf and Clayton H. Heathcock

6. The Synthesis of Indolizidine and Quinolizidine Alkaloids of Tylophora, Cryptocarya, Ipomoea, Elaeocarpus, and Related Species 241

R.B. Herbert

7. Recent Advances in the Total Synthesis of Pentacyclic Aspidosperma Alkaloids 275

Larry E. Overman and Michael Sworin

Volume 4

1. Amphibian Alkaloids: Chemistry, Pharmacology and Biology 1 John W. Daly and Thomas F. Spande

2. Marine Alkaloids and Related Compounds 275 William F enical

Contents of Previous Volumes xv

3. The Dimeric Alkaloids of the Rutaceae Derived by Diels-Alder Addition 331

Peter G. Waterman

4. Teratology of Steroidal Alkaloids Richard F. Keeler

Volume 5

1. The Chemistry and Biochemistry of Simple Indolizidine and

389

Related Polyhydroxy Alkaloids 1 Alan D. Elbein and Russell J. Molyneux

2. Structure and Synthesis of Phenanthroindiolizidine Alkaloids and Some Related Compounds 55

Emery Gellert

3. The Aporphinoid Alkaloids of the Annonaceae 133 Andre Cave, Michel Leboeuf, Peter G. Waterman

4. The Thalictrum Alkaloids: Chemistry and Pharmacology 271 Paul L. Schiff, Jr.

5. Synthesis of Chephalotaxine Alkaloids 639 Tomas Hudlicky, Lawrence D. Kwart, and Josephine W. Reed

Volume 6

1. Chemistry, Biology and Therapeutics of the Mitomycins 1 William A. Remers and Robert T. Dorr

2. Alkaloids of Tabernaemontana Species 75 Teris A. van Beek and Marian A.J. T. van Gessel

3. Advances in Alkaloid Total Synthesis via Iminium Ions, oc-Aminocarbanions and oc-Aminoradicals 227

David J. Hart

4. The Biosynthesis of Proto berberine Alkaloids 297 Christopher W. W. Beecher and William J. Kelleher

5. Quinoline, Acridone and Quinazoline Alkaloids: Chemistry, Biosynthesis and Biological Properties 339

Michael F. Grundon

xvi Contents of Previous Volumes

Volume 7

1. Homoerythrina and Related Alkaloids 1 1. Ralph C. Bick and Sirichai Panichanun

2. Carbon-13 NMR Spectroscopy of Steroidal Alkaloids 43 Pawan K. Agrawal, Santosh K. Srivastava, and William Gaffield

3. Carbon-13 and Proton NMR Shift Assignments and Physical Constants of Norditerpenoid Alkaloids 297

S. William Pelletier and Balawant S. Joshi