Biomimetic Organic Synthesis...Biomimetic Organic Synthesis Edited by Erwan Poupon and Bastien Nay....

Biomimetic Organic Synthesis

Edited by Erwan Poupon and Bastien Nay

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Volume 1Alkaloids


The Editors

Prof. Dr. Erwan PouponUniversite Paris-SudFaculte du Pharmacie5, rue Jean-Baptiste Clement92260 Chatenay-MalabryFrance

Dr. Bastien NayMuseum National d’HistoireNaturelle, CNRS57, rue Cuvier75005 ParisFrance

All books published by Wiley-VCH arecarefully produced. Nevertheless, authors,editors, and publisher do not warrant theinformation contained in these books,including this book, to be free of errors.Readers are advised to keep in mind thatstatements, data, illustrations, proceduraldetails or other items may inadvertently beinaccurate.

Library of Congress Card No.: applied for

British Library Cataloguing-in-PublicationDataA catalogue record for this book is availablefrom the British Library.

Bibliographic information published by theDeutsche NationalbibliothekThe Deutsche Nationalbibliotheklists this publication in the DeutscheNationalbibliografie; detailed bibliographicdata are available on the Internet at<http://dnb.d-nb.de>.

2011 Wiley-VCH Verlag & Co. KGaA,Boschstr. 12, 69469 Weinheim,Germany

All rights reserved (including those oftranslation into other languages). No partof this book may be reproduced in anyform – by photoprinting, microfilm, or anyother means – nor transmitted or translatedinto a machine language without writtenpermission from the publishers. Registerednames, trademarks, etc. used in this book,even when not specifically marked as such,are not to be considered unprotected by law.

Composition Laserwords Private Ltd.,ChennaiPrinting and BindingCover Design Schulz Grafik-Design,Fußgonheim

Printed in the Federal Republic of GermanyPrinted on acid-free paper

ISBN: 978-3-527-32580-1ePDF ISBN: 978-3-527-63477-4ePub ISBN: 978-3-527-63476-7Mobi ISBN: 978-3-527-63478-1

Related Titles

Nicolaou, K. C., Chen, J. S.

Classics in Total Synthesis IIIFurther Targets, Strategies, Methods

2011

ISBN: 978-3-527-32958-8

Dewick, P. M.

Medicinal Natural ProductsA Biosynthetic Approach

Third Edition

2009

ISBN: 978-0-470-74168-9

Dalko, P. I. (ed.)

EnantioselectiveOrganocatalysisReactions and Experimental Procedures

2007

ISBN: 978-3-527-31522-2

Breslow, R. (ed.)

Artificial Enzymes

2005

ISBN: 978-3-527-31165-1

Berkessel, A., Groger, H.

Asymmetric OrganocatalysisFrom Biomimetic Concepts to Applicationsin Asymmetric Synthesis

2005

ISBN: 978-3-527-30517-9

Nicolaou, K. C., Snyder, S. A.

Classics in Total Synthesis IIMore Targets, Strategies, Methods

2003

ISBN: 978-3-527-30684-8


Volume 2Terpenoids, Polyketides, Polyphenols, Frontiers in BiomimeticChemistry


The Editors

Prof. Dr. Erwan PouponUniversite Paris-SudFaculte du Pharmacie5, rue Jean-Baptiste Clement92260 Chatenay-MalabryFrance

Dr. Bastien NayMuseum National d’HistoireNaturelle, CNRS57, rue Cuvier75005 ParisFrance

All books published by Wiley-VCH arecarefully produced. Nevertheless, authors,editors, and publisher do not warrant theinformation contained in these books,including this book, to be free of errors.Readers are advised to keep in mind thatstatements, data, illustrations, proceduraldetails or other items may inadvertently beinaccurate.

Library of Congress Card No.: applied for

British Library Cataloguing-in-PublicationDataA catalogue record for this book is availablefrom the British Library.

Bibliographic information published by theDeutsche NationalbibliothekThe Deutsche Nationalbibliotheklists this publication in the DeutscheNationalbibliografie; detailed bibliographicdata are available on the Internet at<http://dnb.d-nb.de>.

2011 Wiley-VCH Verlag & Co. KGaA,Boschstr. 12, 69469 Weinheim,Germany

All rights reserved (including those oftranslation into other languages). No partof this book may be reproduced in anyform – by photoprinting, microfilm, or anyother means – nor transmitted or translatedinto a machine language without writtenpermission from the publishers. Registerednames, trademarks, etc. used in this book,even when not specifically marked as such,are not to be considered unprotected by law.

Composition Laserwords Private Ltd.,ChennaiPrinting and BindingCover Design Schulz Grafik-Design,Fußgonheim

Printed in the Federal Republic of GermanyPrinted on acid-free paper

ISBN: 978-3-527-32580-1ePDF ISBN: 978-3-527-63477-4ePub ISBN: 978-3-527-63476-7Mobi ISBN: 978-3-527-63478-1

V

Foreword

The beauty and diversity of the biochemical pathways developed by Nature toproduce complex molecules is a good source of inspiration for chemists whowant to guided in their synthetic approach by biomimetic strategies. The firstbiomimetic syntheses were reported at the beginning of the 20th century, with thefamous examples of Collie’s and Robinson’s related to the synthesis of phenolics(orcinol) and alkaloids (tropinone). Since then, the number of reported biomimeticsyntheses, especially in the last twenty years, has increased, demonstrating thepower of these approaches in contemporary organic and bioorganic chemistry.Biomimetic strategies allow the construction of complex natural products in aminimum of steps which is in accordance with the ‘‘atom economy’’ principle ofgreen chemistry and, in addition, simple reagents can be used to access the targets.Furthermore, the bioorganic consequences of such successful syntheses allowthe comprehension of the biosynthetic origin of natural compounds and theseprocesses can produce sufficient quantities of pure products to achieve biologicalinvestigations.

The biomimetic synthesis field came to maturity thanks to interconnexionsbetween biosynthetic studies and organic synthesis, especially in the total synthesisof complex molecules. Biomimetic syntheses could even be considered as thelatest stage of biosynthetic studies, confirming or invalidating the intimate stepsleading to natural product skeletons. For example, the Johnson’s polycyclizationof squalene precursors is one of the most impressive achievements in this field.This is still organic synthesis as the reactions are taking place in the chemist’sflask under chemically controlled experimental conditions, while biosynthetic stepscan involve enzymatic catalysis, at least to a certain extent. However, concerningcomplex biochemical transformations, the exact role of enzymes has not alwaysbeen clear, and has even been questionned by synthetic chemists.

The two book volumes ‘‘Biomimetic Organic Synthesis’’ fill the gap in the organicchemistry literature on complex natural products. These books gather 25 chaptersfrom outstanding authors, not only dealing with the most important familiesof natural products (alkaloids, terpenoids, polyketides, polyphenols. . .), but alsowith biologically inspired reactions and concepts which are truly taking part inbiomimetic processes. By assembling these books, the editors E. Poupon andB. Nay succeeded in gathering specialists in complex natural product chemistry

VI Foreword

for the benefit of the synthetic chemist community. With an educational effortin discussions and schemes, and in comparing both the biosynthetic routes andthe biomimetic achievements, the demonstration of the power of the biomimeticstrategies will become obvious to the readers in both research and teaching areas.These books will be a great source of inspiration for organic chemists and willensure the continued development in this exciting field.

ESPCI-ParisTech Paris, France Janine Cossy

VII

Contents to Volume 1

Preface XVIIList of Contributors XIXBiomimetic Organic Synthesis: an Introduction XXIIIBastien Nay and Erwan Poupon

Part I Biomimetic Total Synthesis of Alkaloids 1

1 Biomimetic Synthesis of Ornithine/Arginine and Lysine-DerivedAlkaloids: Selected Examples 3Erwan Poupon, Rim Salame, and Lok-Hang Yan

1.1 Ornithine/Arginine and Lysine: Metabolism Overview 31.1.1 Introduction: Three Important Basic Amino Acids 31.1.2 From Primary Metabolism to Alkaloid Biosynthesis 51.1.2.1 l-Ornithine Entry into Secondary Metabolism 51.1.2.2 l-Lysine Entry into Secondary Metabolism 5

1.1.3 Closely Related Amino Acids 61.1.4 The Case of Polyamine Alkaloids 71.1.5 Biomimetic Synthesis of Alkaloids 81.2 Biomimetically Related Chemistry of Ornithine- and Lysine-Derived

Reactive Units 91.2.1 Ornithine-Derived Reactive Units 91.2.1.1 Biomimetic Behavior of 4-Aminobutyraldehyde 91.2.1.2 Dimerization 10

1.2.2 Lysine-Derived Reactive Units 111.2.2.1 Oxidative Degradation of Free l-Lysine 111.2.2.2 Clemens Schopf ’s Heritage: 50 Years of Endocyclic Enamines and

Tetrahydroanabasine Chemistry 121.2.2.3 Spontaneous Formation of Alkaloid Skeletons from

Glutaraldehyde 131.2.3 Biomimetic Access to Pipecolic Acids 151.2.3.1 Pipecolic Acids: Biosynthesis and Importance 15

1.2.3.2 Biomimetic Access to Pipecolic Acids 16

VIII Contents

1.3 Biomimetic Synthesis of Alkaloids Derived from Ornithine andArginine 18

1.3.1 Biomimetic Access to the Pyrrolizidine Ring 18

1.3.2 Biomimetic Syntheses of Elaeocarpus Alkaloids 19

1.3.3 Biomimetic Synthesis of Fissoldhimine 22

1.3.4 Biomimetic Synthesis of Ficuseptine, Juliprosine, andJuliprosopine 25

1.3.5 Biomimetic Synthesis of Arginine-Containing Alkaloids:Anchinopeptolides and Eusynstyelamide A 26

1.3.5.1 Natural Products Overview 26

1.3.5.2 Biomimetic Synthesis 26

1.3.6 A Century of Tropinone Chemistry 29

1.4 Biomimetic Synthesis of Alkaloids Derived from Lysine 30

1.4.1 Alkaloids Derived from Lysine: To What Extent? 30

1.4.2 Lupine Alkaloids 31

1.4.2.1 Overview and Biosynthesis Key Steps 31

1.4.2.2 Biomimetic Synthesis of Lupine Alkaloids 32

1.4.2.3 A Biomimetic Conversion of N-Methylcytisine into Kuraramine 33

1.4.3 Biomimetic Synthesis of Nitraria and Myrioneuron Alkaloids 34

1.4.3.1 Biomimetic Syntheses of Nitraramine 35

1.4.3.2 Biomimetic Syntheses of Tangutorine 37

1.4.3.3 Endocyclic Enamines Overview: Biomimetic Observations 39

1.4.4 Biomimetic Synthesis of Stenusine, the Spreading Agent of Stenus

comma 39

1.5 Pelletierine-Based Metabolism 42

1.5.1 Pelletierine: A Small Alkaloid with a Long History 42

1.5.2 Biomimetic Synthesis of Pelletierine and Pseudopelletierine 43

1.5.2.1 Pelletierine (129) 43

1.5.2.2 Pseudopelletierine 44

1.5.3 Lobelia and Sedum Alkaloids 44

1.5.4 Lycopodium Alkaloids 44

1.5.4.1 Overview, Classification, and Biosynthesis 44

1.5.4.2 Biomimetic Rearrangement of Serratinine into Serratezomine A 47

1.5.4.3 Biomimetic Conversion of Serratinine into Lycoposerramine B 47

1.5.4.4 Biomimetic Interrelations within the Lycoposerramine andPhlegmariurine Series 49

1.5.4.5 When Chemical Predisposition Does Not Follow BiosyntheticHypotheses: Unnatural ‘‘Lycopodium-Like’’ Alkaloids 50

1.5.4.6 Total Synthesis of Cermizine C and Senepodine G 51

1.5.4.7 Biomimetic Steps in the Total Synthesis of Fastigiatine 52

1.5.4.8 Biomimetic Steps in the Total Synthesis of Complanadine A 53

References 54

Contents IX

2 Biomimetic Synthesis of Alkaloids Derived from Tyrosine: The Case ofFR-901483 and TAN-1251 Compounds 61Huan Liang and Marco A. Ciufolini

2.1 Introduction 61

2.2 Biomimetic Total Syntheses of FR-901483 and TAN-1251Compounds 63

2.2.1 Snider Synthesis of FR-901483 64

2.2.2 Snider Synthesis of TAN-1251 Substances 67

2.3 Oxidative Amidation of Phenols 71

2.4 Biomimetic Syntheses of FR-901483 and TAN-1251 Compounds via

Oxidative Amidation Chemistry and Related Processes 77

2.4.1 Sorensen Synthesis of FR-901483 78

2.4.2 Honda Synthesis of TAN-1251 Substances 79

2.4.3 Ciufolini Synthesis of FR-901483 and TAN-1251C 80

References 86

3 Biomimetic Synthesis of Alkaloids Derived from Tryptophan:Indolemonoterpene Alkaloids 91Sylvie Michel and Francois Tillequin

3.1 Introduction 91

3.1.1 Indolemonoterpene Alkaloids 91

3.1.2 Classification and Botanical Distribution 91

3.2 Biomimetic Synthesis of Indolomonoterpene Alkaloids with aNon-rearranged Monoterpene Unit: Aristotelia Alkaloids 93

3.3 Biomimetic Synthesis of Secologanin-Derived IndolomonoterpeneAlkaloids 96

3.3.1 Strictosidine, Vincoside, and Simple Corynanthe Alkaloids:Heteroyohimbines and Yohimbines 96

3.3.2 Antirhine Derivatives 99

3.3.3 Conversion of the Corynanthe Skeleton into the Strychnos Skeleton 99

3.3.4 Fragmentation and Rearrangements of Corynanthe Alkaloids:Ervitsine-, Ervatamine-, Olivacine-, and Ellipticine-Type Alkaloids 102

3.3.5 Iboga and Aspidosperma Alkaloids 106

3.3.6 Fragmentation and Rearrangements of Aspidosperma Alkaloids: Vinca

Alkaloids and Rhazinilam 106

3.4 Biomimetic Synthesis of Secologanin-Derived Quinoline

Alkaloids 109

3.5 Biomimetic Synthesis of Dimeric Indolomonoterpene Alkaloids 110

3.5.1 Anhydrovinblastine and the Anticancer Vinblastine Series 110

3.5.2 Strellidimine 113

3.6 Conclusion 113

References 114

X Contents

4 Biomimetic Synthesis of Alkaloids Derived from Tryptophan:Dioxopiperazine Alkaloids 117Timothy R. Welch and Robert M. Williams

4.1 Introduction 1174.2 Prenylated Indole Alkaloids 1174.2.1 Dioxopiperazines Derived from Tryptophan and Proline 1194.2.2 Dioxopiperazine Derived from Tryptophan and Amino Acids other

than Proline 1224.2.3 Bicyclo[2.2.2]diazaoctanes 1264.3 Non-prenylated Indole Alkaloids 1414.3.1 Epidithiodioxopiperazines 1414.4 Conclusion 146

Acknowledgment 147References 147

5 Biomimetic Synthesis of Alkaloids with a Modified Indole Nucleus 149Tanja Gaich and Johann Mulzer

5.1 Introduction 1495.2 Individual Examples 1505.2.1 (±)-Camptothecin 1505.2.2 (±)-Discorhabdins C and E 1545.2.3 (±)-Brevianamides, Paraherquamides, VM55599, and

Marcfortines 1555.2.4 (+)-Stephacidin A and (−)-Stephacidin B 1585.2.5 (±)-Chartelline C 1605.2.6 (+)-Welwitindolinone A and (−)-Fischerindole I 1645.2.7 (−)-Gelselegine 1665.2.8 Communesin, Calycanthines, and Chimonanthines 1685.2.9 (+)-11,11′-Dideoxyverticillin A 1715.2.10 (±)-Borreverine and (±)-Isoborreverine 1735.3 Conclusion 175

References 175

6 Biomimetic Synthesis of Manzamine Alkaloids 181Romain Duval and Erwan Poupon

6.1 Introduction 1816.2 Two Complementary Hypotheses: An ‘‘Acrolein Scenario’’ and a

‘‘Malondialdehyde Scenario’’ 1826.2.1 From Fatty Aldehydes Precursors to Simple 3-Alkyl-Pyridine

Alkaloids 1826.2.2 Biomimetic Synthesis of Dihydropyridines and Dihydropyridinium

Salts 1886.2.3 A Tool Box of Biomimetic C5 Reactive Units from the ‘‘Old’’ Zincke

Reaction 1896.3 Biomimetic Synthesis of Pyridinium Marine Sponge Alkaloids 191

Contents XI

6.3.1 Biomimetic Total Synthesis of Cyclostellettamine B and Related3-Alkylpyridiniums 191

6.3.2 Biomimetic Synthesis of Xestospongins and Related Structures 1916.3.3 Is the Zincke-Type Pyridine Ring-Opening Biomimetic? 1936.3.4 Alkylpyridines with Unusual Linking Patterns 1946.3.4.1 Biomimetic Synthesis of Pyrinodemin A 1946.3.4.2 Biomimetic Synthesis of Pyrinadine A 1956.4 Development of Baldwin’s Hypothesis: From Cyclostellettamines to

Keramaphidin-Type Alkaloids 1956.4.1 Linking Pyridinium Alkaloids and Manzamine A-Type Alkaloids 1956.4.2 Biomimetic Total Synthesis of Keramaphidin B 1976.4.2.1 Model Studies (1994) 1976.4.2.2 Total Synthesis of Keramaphidin B (1998) 1976.4.3 Drawbacks of the ‘‘Acrolein’’ Scenario 1986.4.3.1 Very Low Yield of the Endo-Intramolecular Diels–Alder Reaction 1986.4.3.2 Undesirable Transannular Hydride Transfers 1996.4.3.3 Conversion of a ‘‘Keramaphidin’’ Skeleton into an

‘‘Ircinal/Manzamine’’ Skeleton Was Not Experimentally Possible 2006.5 ‘‘Malondialdehyde Scenario:’’ A Modified Hypothesis Placing

Aminopentadienals as Possible Precursors of ManzamineAlkaloids 200

6.5.1 Keramaphidin/Ircinal Connection 2006.5.2 Halicyclamine Connection 2016.6 Testing the Modified Hypothesis in the Laboratory 2036.6.1 Biomimetic Models toward Manzamine A 2036.6.2 Biomimetic Models toward Halicyclamines 2056.7 Biomimetic Approaches toward Other Manzamine Alkaloids 2086.7.1 Biomimetic Models of Madangamine Alkaloids 2086.7.2 Biomimetic Model of Nakadomarine A 2106.7.3 Biomimetic Models of Sarains: A Side Branch of the Manzamine

Tree 2116.8 A Biomimetic Tool-Box for the Synthesis of Manzamine Alkaloids:

Glutaconaldehydes and Aminopentadienals 2136.9 Biosynthesis of Manzamine Alkaloids: Towards a Universal

Scenario 2156.9.1 From Fatty Acids to Long-Chain Aminoaldehydes and Sarain

Alkaloids 2156.9.2 Pyridine Alkaloids: Theonelladine, Cyclostellettamine, and

Xestospongin-Type Alkaloids 2156.9.3 From Cyclostellettamines to Keramaphidin and

Halicyclamine/Haliclonamine Alkaloids 2186.9.4 Spinal Cord of Manzamine Metabolism: The Ircinal Pathway 2186.9.5 From Ircinal and Pro-ircinals to Manzamine A Alkaloids 2186.9.6 From Pro-ircinals to Madangamine Alkaloids 2186.9.7 From Pro-ircinals to Manadomanzamine Alkaloids 219

XII Contents

6.9.8 From Ircinals and Pro-ircinals to Nakadomarine Alkaloids 2196.10 Total Syntheses of Manzamine-Type Alkaloids 2196.11 Conclusion 220

References 221

7 Biomimetic Synthesis of Marine Pyrrole-2-Aminoimidazole andGuanidinium Alkaloids 225Jerome Appenzeller and Ali Al-Mourabit

7.1 Introduction 2257.1.1 Introduction to Pyrrole-2-Aminoimidazole (P-2-AI) Marine

Alkaloids 2267.1.2 Proposed Biogenetic Hypothesis for Clathrodin (1) and Related

Monomers Starting from α-Amino Acids 2297.2 Ground Work of George Buchi: Dibromophakellin (7) Synthesis from

Dihydrooroidin (31) 2337.3 Biomimetic Synthesis of P-2-AI Linear and Polycyclic

Monomers 2347.3.1 Biomimetic Synthesis of Linear Monomers 2377.3.1.1 Debromodispacamides B (18) and D (39) and Dispacamide

A (4) 2377.3.1.2 Clathrodin (1) and Its Brominated Derivative Oroidin (3) 2377.3.2 Biomimetic Synthesis of Cyclized Monomers 2387.3.2.1 Cyclooroidin (48) 2387.3.2.2 Dibromoagelaspongin (6) 2387.3.2.3 Dibromophakellin (7) and Dibromophakellstatin (69) 2437.3.2.4 Hymenialdisines (91) 2477.3.2.5 Agelastatins 2507.4 Biomimetic Synthesis of P-2-AIs Simple Dimers 2537.4.1 Mauritiamine 2537.4.2 Sceptrins, Ageliferins, and Oxysceptrins 2547.5 Biomimetic Synthesis of Complex Dimers: Palau’amine and Related

Congeners 2557.5.1 Common Chemical Pathway for P-2-AI Biosynthesis 2567.5.2 First Proposal Based on a Diels–Alder Key Step 2577.5.3 Universal Chemical Pathway 2577.5.4 Intramolecular Aziridinium Mediated Mechanism for the Formation

of Massadine (141) from Massadine Chloride (155) 2597.5.5 Aziridinium Mechanism for the Formation of the Tetramer

Stylissadine A 2597.5.6 Synthetic Achievements 2617.5.6.1 Axinellamines A/B 2627.5.6.2 Massadine Chloride (149) and Massadine (135) 2637.5.6.3 Palau’amine (11) 2657.6 New Challenging P-2-AI Synthetic Targets and Perspectives 266

References 267

Contents XIII

8 Biomimetic Syntheses of Alkaloids with a Non-Amino Acid Origin 271Edmond Gravel

8.1 Introduction 2718.2 Galbulimima Alkaloids 2718.2.1 Alkaloids of Class I 2728.2.2 Alkaloids of Class II and Class III 2738.3 Cyclic Imine Marine Alkaloids 275

8.3.1 Symbioimine and Neosymbioimine 2768.3.2 Pinnatoxins and Pteriatoxins 2798.3.3 Gymnodimine and Derivatives 2828.4 Other Polyketide Derived Alkaloids 2848.4.1 Cassiarins A and B 284

8.4.2 Decahydroquinoline Alkaloids 2858.4.3 Zoanthamine Alkaloids 2888.4.4 Azaspiracids 2918.5 Alkaloids Derived from Terpene Precursors 2938.5.1 Cephalostatins and Ritterazines 294

8.5.2 Daphniphyllum Alkaloids 2988.6 Conclusion 305

References 307

9 Biomimetic Synthesis of Azole- and Aryl-Peptide Alkaloids 317Hans-Dieter Arndt, Roman Lichtenecker, Patrick Loos, andLech-Gustav Milroy

9.1 Introduction 3179.1.1 Peptide Alkaloids: An Overview 317

9.1.2 Sources of Peptide Alkaloids 3189.1.3 Key Features of Biosynthesis 3199.2 Azole-Containing Peptide Alkaloids 3219.2.1 Structural Features 3219.2.2 Biomimetic Elements in Azole-Containing Peptide

Alkaloids 323

9.2.3 Thiangazole 3249.2.4 Lissoclinamide 7 3269.2.5 Thiostrepton 3289.2.6 GE2270A 3349.3 Peptide Alkaloids Cyclized by Oxidation of Aryl Side

Chains 3369.3.1 Cyclic Peptides Containing Aryl-Alkyl Ethers 3369.3.2 Cyclic Peptides Containing Biaryl Ethers 3399.3.3 Cyclopeptides Containing Biaryls 3449.3.4 Vancomycin 345

References 350

XIV Contents

10 Biomimetic Synthesis of Indole-Oxidized and Complex PeptideAlkaloids 357Hans-Dieter Arndt, Lech-Gustav Milroy, and Stefano Rizzo

10.1 Indole-Oxidized Cyclopeptides 35710.1.1 Introduction 35710.1.2 TMC-95A–D 35810.1.2.1 Formation of the Trp-Tyr Biaryl Bond by Metal-Catalyzed Cross

Coupling 36110.1.2.2 Stereocontrolled Oxidation of the Oxindole Fragment 36110.1.2.3 Late-Stage Stereoselective (Z)-Enamide Formation 36210.1.3 Celogentin C 36310.1.3.1 Intramolecular Knoevenagel Condensation/Radical Conjugate

Addition 36610.1.3.2 C–H Activation–Indolylation 36710.1.3.3 NCS-Mediated Oxidative Coupling 36810.1.4 Himastatin and Chloptosin 36910.1.4.1 Synthesis of the Himastatin Pyrroloindole Core 37210.1.4.2 Synthesis of the Chloptosin Pyrroloindole Core 37310.1.4.3 Macrolactamization 37310.1.5 Diazonamide 37510.1.5.1 Late-Stage Aromatic Chlorination 37810.1.5.2 Bisoxazole Ring System via Oxidative Dehydrative Cyclization 37910.1.5.3 Oxidative Annulation 37910.1.5.4 Sequential Nucleophilic 1,2-Addition, Electrophilic Aromatic

Substitution 38010.1.5.5 Reductive Aminal Formation 38010.1.5.6 Indole–Indole Coupling 38110.2 A Complex Peptide Alkaloid: Ecteinascidine 743 (ET 743) 38210.2.1 Biosynthesis and Biomimetic Strategy 38310.2.2 Pentacycle Formation 38510.2.3 Bridge Formation 38910.2.4 Endgame 39010.3 Outlook 391

References 392


Part II Biomimetic Synthesis of Terpenoids and PolyprenylatedNatural Compounds 395

11 Biomimetic Rearrangements of Complex Terpenoids 397Bastien Nay and Laurent Evanno

Contents XV

12 Polyprenylated Phloroglucinols and Xanthones 433Marianna Dakanali and Emmanuel A. Theodorakis

Part III Biomimetic Synthesis of Polyketides 469

13 Polyketide Assembly Mimics and Biomimetic Access to AromaticRings 471Gregory Genta-Jouve, Sylvain Antoniotti, and Olivier P. Thomas

14 Biomimetic Synthesis of Non-Aromatic Polycyclic Polyketides 503Bastien Nay and Nassima Riache

15 Biomimetic Synthesis of Polyether Natural Products via PolyepoxideOpening 537Ivan Vilotijevic and Timothy F. Jamison

16 Biomimetic Electrocyclization Reactions toward Polyketide-DerivedNatural Products 591James Burnley, Michael Ralph, Pallavi Sharma, and John E. Moses

Part IV Biomimetic Synthesis of Polyphenols 637

17 Biomimetic Synthesis and Related Reactions of Ellagitannins 639Takashi Tanaka, Isao Kouno, and Gen-ichiro Nonaka

18 Biomimetic Synthesis of Lignans 677Craig W. Lindsley, Corey R. Hopkins, and Gary A. Sulikowski

19 Synthetic Approaches to the Resveratrol-Based Family of OligomericNatural Products 695Scott A. Snyder

20 Sequential Reactions Initiated by Oxidative Dearomatization.Biomimicry or Artifact? 723Stephen K. Jackson, Kun-Liang Wu, and Thomas R.R. Pettus

Part V Frontiers in Biomimetic Chemistry: From Biological toBio-inspired Processes 751

21 The Diels–Alderase Never Ending Story 753Atsushi Minami and Hideaki Oikawa

22 Bio-Inspired Transfer Hydrogenations 787Magnus Rueping, Fenja R. Schoepke, Iuliana Atodiresei, and Erli Sugiono

XVI Contents

23 Life’s Single Chirality: Origin of Symmetry Breaking inBiomolecules 823Michael Mauksch and Svetlana B. Tsogoeva

Part VI Conclusion: From Natural Facts to Chemical Fictions 847

24 Artifacts and Natural Substances Formed Spontaneously 849Pierre Champy

Index 935

VII


Part I Biomimetic Total Synthesis of Alkaloids 1

1 Biomimetic Synthesis of Ornithine/Arginine and Lysine-DerivedAlkaloids: Selected Examples 3Erwan Poupon, Rim Salame, and Lok-Hang Yan

2 Biomimetic Synthesis of Alkaloids Derived from Tyrosine: The Case ofFR-901483 and TAN-1251 Compounds 61Huan Liang and Marco A. Ciufolini

3 Biomimetic Synthesis of Alkaloids Derived from Tryptophan:Indolemonoterpene Alkaloids 91Sylvie Michel and Francois Tillequin

4 Biomimetic Synthesis of Alkaloids Derived from Tryptophan:Dioxopiperazine Alkaloids 117Timothy R. Welch and Robert M. Williams

5 Biomimetic Synthesis of Alkaloids with a Modified Indole Nucleus 149Tanja Gaich and Johann Mulzer

6 Biomimetic Synthesis of Manzamine Alkaloids 181Romain Duval and Erwan Poupon

7 Biomimetic Synthesis of Marine Pyrrole-2-Aminoimidazole andGuanidinium Alkaloids 225Jerome Appenzeller and Ali Al-Mourabit

8 Biomimetic Syntheses of Alkaloids with a Non-Amino Acid Origin 271Edmond Gravel

VIII Contents

9 Biomimetic Synthesis of Azole- and Aryl-Peptide Alkaloids 317Hans-Dieter Arndt, Roman Lichtenecker, Patrick Loos, andLech-Gustav Milroy

10 Biomimetic Synthesis of Indole-Oxidized and Complex PeptideAlkaloids 357Hans-Dieter Arndt, Lech-Gustav Milroy, and Stefano Rizzo


Preface XVIIList of Contributors XIXBiomimetic Organic Synthesis: an Introduction XXIIIBastien Nay and Erwan Poupon

Part II Biomimetic Synthesis of Terpenoids and PolyprenylatedNatural Compounds 395

11 Biomimetic Rearrangements of Complex Terpenoids 397Bastien Nay and Laurent Evanno

11.1 Introduction 397

11.2 Beginning with Monoterpene Rearrangements 397

11.2.1 Historical Overview of Monoterpene Rearrangements: A Century sinceWagner’s Structure of Camphene 397

11.2.2 Kinetics of the Monoterpene Rearrangement and Relation with theCatalytic Landscape in Terpene Biosynthesis 399

11.3 Biomimetic Rearrangements of Sesquiterpenes 401

11.3.1 Caryophyllenes in Sesquiterpene Biosyntheses 401

11.3.2 Biomimetic Studies in the Caryolane and Clovane Series 402

11.3.3 Biomimetic Studies in the Triquinane Series 404

11.3.4 Oxidative Rearrangements in the Silphinane Series: thePenifulvins 405

11.3.5 Miscellaneous Sesquiterpene Rearrangements 406

11.4 Diterpene Rearrangements 408

11.4.1 Dead End Products in the Biomimetic Synthesis of Antheridic Acidfrom Gibberellins 408

11.4.2 Biomimetic Synthesis of Marine Diterpenes from Pseudopterogorgia

elisabethae 410

11.4.3 Biomimetic Relationships among Furanocembranoids 414

11.4.4 Miscellaneous Diterpenes 417

11.5 Triterpene Rearrangements 420

Contents IX

11.6 Some Examples of the Biomimetic Synthesis ofMeroterpenoids 424

11.7 Conclusion 425References 428

12 Polyprenylated Phloroglucinols and Xanthones 433Marianna Dakanali and Emmanuel A. Theodorakis

12.1 Introduction 43312.2 Polycyclic Polyprenylated Phloroglucinols 43312.2.1 Introduction and Chemical Classification 43312.2.2 Biosynthesis of PPAPs 43412.2.3 Biomimetic Synthesis of PPAPs 43612.2.3.1 Biomimetic Total Synthesis of (±)-Clusianone 43812.2.3.2 Biomimetic Approach to the Bicyclic Framework of Type A

PPAPs 43912.2.3.3 Biomimetic Synthesis of (±)-Ialibinone A and B and

(±)-Hyperguinone B 44012.2.4 Non-biomimetic Synthesis of PPAPs 44112.2.4.1 Total Synthesis of Garsubellin A 44112.2.4.2 Total Synthesis of Nemorosone and Clusianone through

Differentiation of ‘‘Carbanions’’ 44312.2.4.3 Total Synthesis of (−)-Hyperforin 44512.2.4.4 Total Synthesis of Clusianone 44812.2.5 Concluding Remarks 45112.3 Polyprenylated Xanthones 45212.3.1 Introduction and Chemical Classification 45212.3.2 Biosynthesis of Polyprenylated Xanthones 45412.3.3 Biomimetic Synthesis of Caged Garcinia Xanthones 45512.3.3.1 Nicolaou Approach to Forbesione and Gambogin 45812.3.3.2 Theodorakis’ Unified Approach to Caged Garcinia

Xanthones 45912.3.3.3 Synthesis of Methyllateriflorone 45912.3.3.4 Non-biomimetic Synthesis of the Caged Garcinia

Xanthones 46012.3.3.5 Concluding Remarks 463

References 464

Part III Biomimetic Synthesis of Polyketides 469

13 Polyketide Assembly Mimics and Biomimetic Access to AromaticRings 471Gregory Genta-Jouve, Sylvain Antoniotti, and Olivier P. Thomas

13.1 Introduction 47113.2 Polyketide Assembly Mimics 47213.2.1 Type-a Mimics 475

X Contents

13.2.1.1 Malonyl Activation 47513.2.1.2 Without Malonyl Activation 47713.2.2 Type-b Mimics 47813.2.2.1 Malonyl Activation 47913.2.2.2 Without Malonyl Activation 48213.2.3 Type-c Mimics 48313.3 Biomimetic Access to Aromatic Rings 48513.3.1 Biomimetic Access to Benzenoid Derivatives 48713.3.2 Biomimetic Access to Naphthalenoid Derivatives 49213.3.3 Biomimetic Access to Anthracenoid Derivatives 49413.3.4 Biomimetic Access to Tetracyclic Derivatives 49513.3.4.1 Biomimetic Access to Tetracenoid Derivatives 49513.3.4.2 Biomimetic Access to Tetraphenoid Derivatives 49613.3.4.3 Biomimetic Access to Benzo[a]tetracenoid Derivatives 49813.4 Conclusion 499

References 499

14 Biomimetic Synthesis of Non-Aromatic Polycyclic Polyketides 503Bastien Nay and Nassima Riache

14.1 Introduction 50314.2 Biomimetic Studies in the Nonadride Series 50414.2.1 Dimerization Process towards Isoglaucanic Acid 50414.2.2 The Unresolved Case of CP-225917 and CP-263114 50514.3 Biomimetic Syntheses Involving the Diels–Alder Reaction 50614.3.1 Biomimetic Diels–Alder Reactions Affording Decalin Systems 50614.3.2 Biomimetic Diels–Alder Reactions Affording Tetrahydroindane

Systems 50914.3.3 Biomimetic Diels–Alder Reactions Affording Spiro Systems 51214.3.4 Biomimetic TADA Reactions toward FR182877, Hexacyclinic Acid and

the Parent Cochleamycin A and Macquarimicin A 51414.3.5 Biomimetic TADA Reactions toward Spinosyns 52114.4 Biomimetic Cascade Reactions 52414.4.1 A Metalated Ionophore Template for the Biomimetic Synthesis of

Tetronasin 52414.4.2 The 6,5,6-Fused System and Macrocycle of Hirsutellones: Work Yet to

Be Done? 52514.5 Conclusion 530

References 530

15 Biomimetic Synthesis of Polyether Natural Products via PolyepoxideOpening 537Ivan Vilotijevic and Timothy F. Jamison

15.1 Introduction 53715.2 Synthetic Considerations: Baldwin’s Rules 538

Contents XI

15.2.1 Control of Regioselectivity in Intramolecular Epoxide-OpeningReactions 539

15.3 Polycyclic Polyethers: Structure and Biosynthesis 53915.3.1 Polyether Ionophores 53915.3.2 Polyethers Derived from Squalene 54215.3.3 Ladder Polyethers 54515.4 Epoxide-Opening Cascades in the Synthesis of Polycyclic

Polyethers 55015.4.1 Epoxide-Opening Cascades in the Synthesis of Polyether

Ionophores 55015.4.2 Applications of Epoxide-Opening Cascades in the Synthesis of

Ionophores 55415.4.3 Epoxide-Opening Cascades in the Synthesis of Squalene-Derived

Polyethers 55815.4.4 Epoxide-Opening Cascades in the Synthesis of Ladder Polyethers 56515.4.4.1 Iterative Approaches 56515.4.4.2 Epoxide-Opening Cascades Leading to Fused Polyether Systems 56715.4.4.3 Applications of Epoxide-Opening Cascades in the Synthesis of Ladder

Polyethers 58015.5 Summary and Outlook 583

References 584

16 Biomimetic Electrocyclization Reactions toward Polyketide-DerivedNatural Products 591James Burnley, Michael Ralph, Pallavi Sharma, and John E. Moses

16.1 Introduction 59116.2 Electrocyclic Reactions 59216.3 Polyketides 59316.4 Fatty Acid Biosynthesis 59416.5 Biomimetic Analysis 59716.6 6π Electrocyclizations 59816.6.1 Tridachiahydropyrones 59916.6.2 Tridachione Family 60316.6.3 Pseudorubrenoic Acid A 60816.6.4 Torreyanic Acid 61016.7 8π Systems and the Black 8π –6π Electrocyclic Cascade 61216.7.1 Endiandric Acids 61216.7.2 Nitrophenyl Pyrones: SNF4435 C and D 61816.7.3 Ocellapyrones 62116.7.4 Elysiapyrones 62416.7.5 Shimalactones 62516.8 Biological Electrocyclizations and Enzyme Catalysis 62816.9 Conclusion 631

Acknowledgments 632References 632

XII Contents

Part IV Biomimetic Synthesis of Polyphenols 637

17 Biomimetic Synthesis and Related Reactions of Ellagitannins 639Takashi Tanaka, Isao Kouno, and Gen-ichiro Nonaka

17.1 Introduction 63917.2 Biosynthesis of Ellagitannins 64117.3 Biomimetic Total Synthesis of Ellagitannins 64217.3.1 Chemical Synthesis of Ellagitannins by Biaryl Coupling of Galloyl

Esters 64217.3.2 Ellagitannins with 1C4 Glucopyranose Cores 64517.3.3 Synthesis of an Allagitannin with 3,6-(R)-HHDP Group 65117.3.4 Synthesis of Ellagitannins by Double Esterification of

Hexahydroxydiphenic Acid 65117.3.5 Biomimetic Synthesis of Dimeric Ellagitannin 65817.4 Conversion of Dehydroellagitannins into Related Ellagitannins 65917.4.1 Reduction of DHHDP Esters 65917.4.2 Reaction with Thiol Compounds and the Biomimetic Synthesis of

Chebulagic Acid 66217.4.3 Other Reactions of DHHDP Esters 66317.5 Reactions of C-Glycosidic Ellagitannins 66317.5.1 Conversion between Pyranose-Type Ellagitannins and C-Glycosidic

Ellagitannins 66517.5.2 Reaction at the C1 Positions of C-Glycosidic Ellagitannins 66517.5.3 Oxidation of C-Glycosidic Ellagitannins 66917.6 Conclusions and Perspectives 670

References 672

18 Biomimetic Synthesis of Lignans 677Craig W. Lindsley, Corey R. Hopkins, and Gary A. Sulikowski

18.1 Introduction to Lignans 67718.1.1 Biomimetic Synthesis of Lignans 68118.1.1.1 Biomimetic Synthesis of Podophyllotoxin-Like Lignans 68118.1.1.2 Biomimetic Synthesis of Furofuran Lignans 68118.1.1.3 Biomimetic Synthesis of Benzoxanthenone Lignans 68318.1.1.4 Biomimetic Synthesis of Benzo[kl]xanthene Lignans 68618.2 Conclusion 688

References 691

19 Synthetic Approaches to the Resveratrol-Based Family of OligomericNatural Products 695Scott A. Snyder

19.1 Introduction 69519.2 Biosynthetic Approaches 69719.3 Stepwise Synthetic Approaches 70519.3.1 Work toward Single Targets within the Resveratrol Family 705

Contents XIII

19.3.2 Towards a Universal, Controlled Synthesis Approach 70919.4 Conclusions 717

Acknowledgments 717References 718

20 Sequential Reactions Initiated by Oxidative Dearomatization.Biomimicry or Artifact? 723Stephen K. Jackson, Kun-Liang Wu, and Thomas R.R. Pettus

20.1 Overview 72320.2 Oxidative Dearomatization Sequences and the Initial

Intermediate 72320.3 Intermolecular Dimerizations 72420.4 Successive Intermolecular Reactions 72720.5 Intramolecular Cycloadditions 72920.6 Other Successive Intramolecular Cascade Sequences 73120.7 Successive Tautomerizations and Rearrangements 73320.8 Sequential Ring Rupture and Contraction 73720.9 Sequential Ring Rupture and Expansion 73920.10 Successive Intramolecular and Intermolecular Reactions 74120.11 Natural Products Hypothesized to Conclude Phenol Oxidative

Cascades 74120.12 Conclusion 747

References 747

Part V Frontiers in Biomimetic Chemistry: From Biological toBio-inspired Processes 751

21 The Diels–Alderase Never Ending Story 753Atsushi Minami and Hideaki Oikawa

21.1 Introduction 75321.2 Diels–Alderases Found in Nature 75421.2.1 Lovastatin Nonaketide Synthase 75521.2.2 Macrophomate Synthase 75621.2.3 Solanapyrone Synthase 75821.3 Intramolecular Diels–Alder Reactions Possibly Catalyzed by

Dehydratase or DH-Red-Domain of PKS or Hybrid PKS-NRPS 76021.3.1 Equisetin and Chaetoglobosin (Compactin, Lovastatin,

Solanapyrone) 76121.3.2 Kijanimicin, Chlorothricin, and Tetrocarcin A 76321.3.3 Indanomycin 76421.3.4 Spinosyn 76621.4 Diels–Alder Reactions after Formation of Reactive Substrates by

Oxidation Enzymes 76721.4.1 Oxidation of Phenol and Catechol to Reactive Dienone and

Orthoquinone 768

XIV Contents

21.4.2 Conjugated Diene Derived from Dehydrogenation of Prenyl SideChain 775

21.4.3 Cyclopentadiene Formation Derived from Dehydrogenation 77921.5 Summary 779

References 782

22 Bio-Inspired Transfer Hydrogenations 787Magnus Rueping, Fenja R. Schoepke, Iuliana Atodiresei, and Erli Sugiono

22.1 Introduction 78722.2 Nature’s Reductions: Dehydrogenases as a Role Model 78722.3 Brønsted Acid Catalyzed Transfer Hydrogenation of Imines, Imino

Esters, and Enamines 78822.4 Asymmetric Organocatalytic Reduction of N-Heterocycles 80022.4.1 Asymmetric Organocatalytic Reduction of Quinolines 80022.4.2 Asymmetric Brønsted Acid Catalyzed Hydrogenation of Indoles 80522.4.3 Asymmetric Brønsted Acid Catalyzed Hydrogenation of Benzoxazines,

Benzothiazines, Benzoxazinones, Quinoxalines, Quinoxalinones,Diazepines, and Benzodiazepinones 806

22.4.4 Asymmetric Organocatalytic Reduction of Pyridines 81322.5 Asymmetric Organocatalytic Reductions in Cascade Sequences 81422.6 Conclusion 817

References 818

23 Life’s Single Chirality: Origin of Symmetry Breaking inBiomolecules 823Michael Mauksch and Svetlana B. Tsogoeva

23.1 Introduction 82323.2 Autocatalytic Enantioselective Reactions 82523.3 Autocatalysis and Self-replication 83323.4 Polymerization and Aggregation Models of Enantioenrichment 83423.5 Phase Equilibria 83523.6 Adsorption on Chiral Surfaces 83723.7 Spontaneous Symmetry Breaking in Conglomerate

Crystallizations 83723.8 Symmetry Breaking in Reaction–Diffusion Models, Collision Kinetics,

and Membrane Diffusion 84023.9 Concluding Remarks and Outlook 840

References 841

Part VI Conclusion: From Natural Facts to Chemical Fictions 847

24 Artifacts and Natural Substances Formed Spontaneously 849Pierre Champy

24.1 Introduction 84924.2 Glucosidases as Triggers for Formation of By-products 852

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