Plant Secondary Metabolism Ine of Plant Secondary Metabolism

Plant Secondary Metabolism ine of Plant Secondary Metabolism

chlorophyll + C02 + light cyclitols, polyols photosynthesis^

C6C1-compounds glycosides t carbohydrates pentose phosphate shikimi c acid erythrose 4-phosphate I glycolysis chorismic acid phosphoenol pyruvate

£so-chorismic cyanogenic glycosides acid * glucosinolates peptides • proteins non-protein amino acids

f tricarboxyli c acid amino acids cycle acids

te n id alkaloids r^ ° alkaloids s- ternenes ^ roev . .

^ ^ / / waxes

I acetylenes

rotenoids / hydrocarbons flavonoids polyketides • phenols phenylpropanoid \ naphthoquinones coumarins compounds \ anthraquinones Iigni n lignans condensed tannins Plant Secondary Metabolism

]David S. Seigler Department of Plant Biology University of Illinois, Urbana

SPRINGER SCIENCE+BUSINESS MEDIA, LLC Library of Congress Cataloging-in-Publication Data

Seigler, David S. Plant secondary metabolism / David S. Seigler. p. em. Includes bibliographical references. ISBN 978-1-4613-7228-8 ISBN 978-1-4615-4913-0 (eBook) DOI 10.1007/978-1-4615-4913-0 1. Plants--Metabolism. 2. Metabolism, Secondary. 3. Botanical chemistry. r. Title. QK887.538 1995 581.1'33--DC20 89-70112 CIP

Copyright © 1998 by Springer Science+Business Media New York Originally published by Kluwer Academic Publishers in 1998 Softcm-er reprint of the hardcover 1st edition 1998 All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form, or by any means, mechanical, photocopying, recording, or otherwise, without the prior written permission of the publisher.

Printed on acid-free paper.

This printing is a digital duplication of the original edition. Table of Contents

Preface vii Chapter 21 Sesquiterpenes 367 Acknowledgments ix Chapter 22 Diterpenes and Sesterterpenes 398 Chapter 1 Introduction 1 Chapter 23 Triterpenes and Steroids 427 Chapter 2 Fatty Acids 16 Chapter 24 Saponins and Cardenolides 456 Chapter 3 Acetylenic Compounds 42 Chapter 25 Limonoids, Quassinoid., and Related Chapter 4 Plant Waxes 51 Compound. 473 Chapter 5 Polyketides 56 Chapter 26 Tetraterpenes or Carotenoids 486 Chapter 6 Benzoquinones, Naphthquinones, and Chapter 27 Introduction to Alkaloids 506 Anthraquinones 76 Chapter 28 Simple Amines, Simple Aromatic and Chapter 7 Shikimic Acid Pathway 94 Pyridine Alkaloids 513 Chapter 8 Phenylpropanoids 106 Chapter 29 Pyrrolidine, Tropane, Piperidine, and Chapter 9 Coumarins 130 Polyketide Alkaloids 531 Chapter 10 2-Pyrones, Stilbenes, Chapter 30 Pyrrolizidine, Quinolizidine, and Dihydrophenanthrenes, and Xanthones 139 Indolizidine Alkaloids 546 Chapter 11 F1avonoids 151 Chapter 31 Alkaloids Derived from Anthranilic Chapter 12 Tanuins 193 Acid 568 Chapter 13 Nonprotein Amino Acids 215 Chapter 32 Isoquinoline and Benzylisoquinoline Chapter 14 Peptide. 234 Alkaloids 578 Chapter 15 Carbohydrate. 247 Chapter 33 Alkaloids Derived from Both Tyrosine Chapter 16 Cyanogenic Glycosides and and Phenylalanine 617 Cyanolipids 273 Chapter 34 Indole Alkaloids 628 Chapter 17 Glucosinolates 300 Chapter 35 Ergot and Other Indole Alkaloids 655 Chapter 18 Introduction to Terpenes 312 Chapter 36 Alkaloids of Terpenoid Origin 668 Chapter 19 Monoterpenes 324 Chapter 37 Miscellaneous Types of Alkaloids 692 Chapter 20 Iridoid Monoterpenes 353 Index 713 Preface

Life has evolved as a unified system; no organism exists similar role also has been suggested for fatty acids from alone, but each is in intimate contact with other organisms cyanolipids. Nonprotein amino acids, cyanogenic glyco• and its environment. Historically, it was easier for workers sides, and the non-fatty-acid portion of cyanolipids also are in various disciplines to delimit artificially their respective incorporated into primary metabolites during germination. areas of research, rather than attempt to understand the entire Secondary metabolites of these structural types are accumu• system of living organisms. This was a pragmatic and neces• lated in large quantities in the seeds of several plant groups sary way to develop an understanding for the various parts. where they probably fulfill an additional function as deter• We are now at a point, however, where we need to investi• rents to general predation. gate those things common to the parts and, specifically, those The second type of relationship involves interaction of things that unify the parts. The fundamental aspects of many plants with other organisms and with their environment. Bio• of these interactions are chemical in nature. Plants constitute logical interactions must be viewed in the light of evolution• an essential part of all life systems; phytochemistry provides ary change and the coadaptation, or perhaps coevolution, of a medium for linking several fields of study. organisms. A plant that possesses the ability to synthesize It is partially through teaching a course in phytochemistry a compound that disturbs the physiological functions of a that I have come to realize more fully the potential of phyto• herbivore may have a selective advantage over one that does chemical studies to unite and integrate a vast amount of not. The chemical abilities of the plant may be utilized to material from different disciplines. The diversity of students establish interlocking relationships within the contexts of that have taken this course and their research interests also pollination, seed dispersal, establishment of mycorrhizal reflects the utility and value of this type of information. fungi, or protection of the plant by another organism, such Among the fields represented are Biology (Ecology, Ento• as ants. The "advantage" gained from such interactions may mology, Plant Biology, Botany, Physiology, Microbiology, be offset by metabolic cost or self-toxicity, but the process and Zoology), Geology (Organic Geochemistry), Chemistry of natural selection optimizes these interacting factors. Thus, (Organic Chemistry, Biochemistry, and Analytical Chemis• assuming the system remains stable for a sufficient time, try), Agriculture (Horticulture, Animal Science, Dairy Sci• eqnilibrium will be reached. Finally, it must be remembered ence, Forestry, Agronomy, and Plant Pathology), Veterinary Medicine, and Food Science. Possibly because of the diffi• that all organisms in a given system are evolving. Interacting culties involved in integrating such a diversity of interests, organisms have the ability to adapt to changes in plant chem• no adequate text presently exists for this course. istry and morphology, and may eventually ntilize plant hosts In this text, I propose to survey our present knowledge that were formerly unacceptable. Host selection, food prefer• of the phytochemistry and the role that secondary metabo• ences, taste, toxicity, wounding responses, allelopathy, and a lites play in biological relationships. These relationships bas• vast array of other topics are the results of these evolutionary ically fall into two categories: the first concerns the function processes. and value of the compounds within the plants themselves. An understanding of the biosynthetic pathways leading Many compounds are catabolized for energy or used to fulfill to secondary metabolites and a recognition of the chemical other requirements that involve nitrogen. For example, fatty structural types present and their distribution among plant acids from triglycerides have long been recognized as energy groups have proven useful for the study of biosystematic sources for the embryo of a germinating seed. Recently, a problems and for achieving an understanding of plant phylo-

vii viii Preface geny. The predictive value of chemotaxonomic information sects, marine organisms, bacteria, fungi, and other organisms has been recognized by natural products chemists. has been incorporated where warranted. Plant secondary compounds play an important role in in• No attempt has been made to reference exhaustively all dustry and medicine. Many industries are based on flavoring information cited in the text. Many references given are to agents and perfumes, rubber, and naval stores. Several sec• review articles and in many instances are not those of the ondary compounds are physiologically active, which results workers who carried out the original work. Although an at• in their use as insecticides, medicinal agents, or biological tempt has been made to give the structures of most com• probes or "tools." Plant compounds that are toxic to man pounds given in the text, some are not included. Further, the and domestic livestock are widespread and may be responsi• structures of some representative compounds are included ble not only for accidental but also for chronic poisoning by in figures, but, as they are not specifically cited in the text, common foods such as cassava, sago, lima, and fava beans. they are not given numbers. Subjects are grouped on the basis of major chemical struc• I apologize to authors inadvertently misquoted and will tural types. Each will be discussed in terms of biosynthesis attempt to correct errors in any future editions. As it is diffi• and distribution, diversity of known structures, taxonomic cult to locate many references dealing with topics discussed application, biological function, toxicity, and medicinal and in this text, I solicit comments and any pertinent information industrial uses. I do not present an encyclopedic coverage that may be useful for correction of errors or for the prepara• of all available literature. Rather, the goal is a readable, inte• tion of further editions and wish to thank those who have grated text that will be suitable for instruction at the ad• already provided me with manuscripts, reprints, unpublished vanced undergraduate as well as the graduate level. In gen• material, suggestions, and assistance in preparing this pres• eral, only phytochemical (Le., plant chemical) data has been ent manuscript. ffitimately, of course, I stand responsible included, although information about the chemistry of in- for the conclusions and statements made in this text. Acknowledgments

I wish to thank Anita Brinker, H. David Clarke, Ute Ecken­ David C. Breeden, Anita Brinker, Stacie E. Canaan, H. bach, Richard Lindroth, Karin Readel, and Kurt Potgieter David Clarke, Paul R. Connelly, Katherine Dowd, Thomas for reading earlier versions of portions or the entire manu­ Dudman, Nicole Duffee, Candace Easter, Robert J. Eilers, script and making suggestions for improvement. The techni­ John Gerlits, Peter Gottschalk, Mark Hediger, Ellen Hei­ cal assistance of Susan Gibbons, Elizabeth Bartlett, Cheryl ninger, Tricia HooChung, Han-Young Kang, Frederick J. Frankfater, Nathaniel Ohler, and Ulrike Nolte also is greatly Lang, Wei Jane Liao, Hengchen Lin, Vincent Ling, Randall appreciated. The comments of J. Balsevich, K. Brown, S. A. Lovell, John Martini, Susan McCarthy, John Ng, James A. Brown, E. E. Conn, K. R. Downum, G. Cordell, D. Gian­ Nitao, Paul Ode, Mark S. Pavlin, Raymond Pedersen, Char­ nasi, J. Gershenzon, J. B. Harbome, E. Leistner, S. Mole, lotte Read, Karin Readel, Nelson T. Rotto, Claire Rutledge, A. Nahrstedt, R. G. Powell, P. Reichard, G. A. Rosenthal, Michael J. Sophia, Andrew L. Staley, Larry J. Thompson, T. J. Simpson, K. Schreiber, P. Waterman, and anonymous Martin B. Wolk, and Craig M. vanZyl. reviewers have been extremely useful in revising the manu­ This work would not be possible if it were not for some script. Greg Payne of Chapman & Hall has provided many of my former teachers and mentors including Allie Marie helpful suggestions. Hobbs, Donald Hamm, Jordan J. Bloomfield, Leon Cieres­ In a number of cases, topics were reviewed in term p'apers zko, Eric Conn, Dale M. Smith and Tom Mabry. submitted by students of the Plant Secondary Metabolites I also wish to express my appreciation to my wife Janice or the Chemical Ecology course. Information from these for her patience during the preparation of this book. She bas papers was extremely helpful and I especially wish to thank assisted in many ways to further this work. the following stndents: John Andersen, Du-Jong Baek,

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