Chemical Synthesis of Hormones,Pheromones and Other Bioregulators

KENJI MORIEmeritus Professor, The University of Tokyo, Japan

A John Wiley and Sons, Ltd., Publication

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Chemical Synthesis of Hormones,Pheromones and Other Bioregulators

Postgraduate Chemistry Series

The Postgraduate Chemistry Series of advanced textbooks is designed to provide a broad understandingof selected growth areas of chemistry at postgraduate student and research level. Volumes concentrateon material in advance of a normal undergraduate text, although the relevant background to a subjectis included. Key discoveries and trends in current research are highlighted, and volumes are extensivelyreferenced and cross-referenced. Detailed and effective indexes are an important feature of the series. Insome universities, the series will also serve as a valuable reference for final year honours students.

Editorial Board

Professor James Coxon (Editor-in-Chief), Department of Chemistry, University of Canterbury,New Zealand

Professor Margaret Brimble, Department of Chemistry, The University of Auckland, New Zealand

Professor Les Field, School of Chemistry, University of New South Wales, Australia

Professor Dr. John Gladysz, Department of Chemistry, Texas A&M University, USA

Professor Karl Hale, School of Chemistry and Chemical Engineering, Queens University Belfast, UK

Titles in the Series

Practical Biotransformations: A Beginners GuideGideon Grogan

Photochemistry of Organic Compounds: From Concepts to PracticePetr Klan and Jakob Wirz

Catalysis in Asymmetric Synthesis, 2nd EditionVittorio Caprio and Jonathan Williams

Reaction Mechanisms in Organic SynthesisRakesh Parashar

Stoichiometric Asymmetric SynthesisMark Rizzacasa and Michael Perkins

Organic Synthesis using Transition MetalsRod Bates

Organic Synthesis with CarbohydratesGeert-Jan Boons and Karl J. Hale

Protecting Groups in Organic SynthesisJames R. Hanson

Chemical Synthesis of Hormones,Pheromones and Other Bioregulators

KENJI MORIEmeritus Professor, The University of Tokyo, Japan

A John Wiley and Sons, Ltd., Publication

This edition first published 2010c 2010 John Wiley & Sons Ltd

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Library of Congress Cataloging-in-Publication Data

Mori, K. (Kenji), 1935Chemical synthesis of hormones, pheromones, and other bioregulators / Kenji Mori.

p. ; cm.Includes bibliographical references and index.ISBN 978-0-470-69724-5 (cloth)ISBN 978-0-470-69723-8 (pbk.) 1. Bioorganic

chemistry. 2. BiomoleculesSynthesis. 3. HormonesSynthesis. 4. PheromonesSynthesis. 5. Plant hormonesSynthesis. I. Title.

[DNLM: 1. Hormoneschemical synthesis. 2. Biological Factorschemicalsynthesis. 3. Pheromoneschemical synthesis. WK 102 M854c 2010]

QD415.M67 2010571.74dc22

2010013112

A catalog record for this book is available from the British Library.

ISBN: 978-0-470-69724-5 (h/b) 978-0-470-69723-8 (p/b)

Set in 10/12pt Times-Roman by Laserwords Private Limited, Chennai, IndiaPrinted in Great Britain by Antony Rowe Ltd, Chippenham, Wiltshire

www.wiley.com

Contents

Preface xiAbbreviations xiii

1 IntroductionBiofunctional Molecules and Organic Synthesis 11.1 What are biofunctional molecules? 11.2 Developmental stages of studies on biofunctional molecules 11.3 Small amounts of the samples are now sufficient for the elucidation

of the structures of biofunctional molecules 31.4 Why must biofunctional molecules be synthesized? 41.5 How can we synthesize biofunctional molecules? 5

1.5.1 What is synthesis? 51.5.2 What kind of consideration is necessary before starting a synthesis? 51.5.3 Synthon 61.5.4 Molecular symmetry and synthesis 61.5.5 Criteria for A Good Synthesis 6

1.6 What kind of knowledge and techniques are necessary to synthesizebiofunctional molecules? 101.6.1 Stereochemistry and reactivity 101.6.2 Stereochemistry and analytical methods 11References 16

2 Synthesis of Phytohormones, Phytoalexins and Other BiofunctionalMolecules of Plant Origin 19

2.1 Phytohormones 192.1.1 What are phytohormones? 192.1.2 Gibberellins 202.1.3 Diterpenes related to gibberellins 302.1.4 Abscisic acid and its relativessynthesis of optically active compounds 382.1.5 Brassinosteroids 412.1.6 Phyllanthrinolactone, a leaf-closing factor 45

2.2 Phytoalexins 492.2.1 What are phytoalexins? 492.2.2 Synthesis of pisatin 492.2.3 Synthesis of 2-(4-hydroxyphenyl)naphthalene-1,8-dicarboxylic anhydride 522.2.4 Synthesis of oryzalexins 532.2.5 Synthesis of phytocassanes 56

vi Contents

2.3 Plant allelochemicals 592.3.1 Synthesis of glycinoeclepin A 592.3.2 Synthesis of strigolactones 61

2.4 Other bioactive compounds of plant origin 672.4.1 Synthesis of arnebinol 672.4.2 Synthesis of magnosalicin 682.4.3 Synthesis of hernandulcin 692.4.4 Synthesis of O-methyl pisiferic acid 712.4.5 Synthesis of diospyrin 732.4.6 Synthesis of mispyric acid 73References 77

3 Synthesis of Insect Bioregulators Other than Pheromones 813.1 Insect juvenile hormones 81

3.1.1 What are insect hormones? 813.1.2 Synthesis of juvabione 823.1.3 Synthesis of the racemates of juvenile hormones 863.1.4 Synthesis of the enantiomers of juvenile hormones 88

3.2 Insect antifeedants 953.2.1 Synthesis of polygodial 953.2.2 Synthesis of warburganal 973.2.3 Synthesis of 3,4-dihydroxypropiophenone 3--d-glucopyranoside 973.2.4 Synthesis of homogynolide A 99

3.3 Insect repellents 1003.3.1 Synthesis of rotundial 1003.3.2 Synthesis of polyzonimine 102References 104

4 Synthesis of Pheromones 1074.1 What are pheromones? 1074.2 Methods for enantioselective synthesis 107

4.2.1 Derivation from enantiopure natural products 1084.2.2 Enantiomer separation (optical resolution) 1084.2.3 Asymmetric synthesis 1094.2.4 Determination of enantiomeric purity 109

4.3 Why is it meaningful to synthesize enantiopure pheromones? 1104.3.1 Determination of absolute configuration (1). trogodermal 1114.3.2 Determination of absolute configuration (2). hemiacetal pheromone

of Biprorulus bibax 1114.3.3 Determination of absolute configuration (3). sesquiterpene pheromone

of Eysarcoris lewisi 1184.3.4 Clarification of the relationship between absolute configuration and pheromone

activityexo-brevicomin 1224.3.5 Clarification of structure (1). lineatin 1244.3.6 Clarification of structure (2). American cockroach pheromone 126

Contents vii

4.3.7 Clarification of structure (3). acoradiene 1294.3.8 Clarification of structure (4). himachalene-type pheromone 1304