Cycloaddition Reactions in Organic Synthesis
.pdfCycloaddition Reactions in Organic Synthesis.
Edited by S. Kobayashi and K. A. Jorgensen Copyright © 2001 Wiley-VCH Verlag GmbH ISBNs: 3-527-30159-3 (Hardcover); 3-527-60025-6 (Electronic)
Shu Kobayashi
Karl Anker Jørgensen (Eds.)
Cycloaddition Reactions
in Organic Synthesis
Cycloaddition Reactions in Organic Synthesis.
Edited by S. Kobayashi and K. A. Jorgensen
Copyright © 2001 Wiley-VCH Verlag GmbH
ISBNs: 3-527-30159-3 (Hardcover); 3-527-60025-6 (Electronic)
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Cycloaddition Reactions in Organic Synthesis.
Edited by S. Kobayashi and K. A. Jorgensen
Copyright © 2001 Wiley-VCH Verlag GmbH
ISBNs: 3-527-30159-3 (Hardcover); 3-527-60025-6 (Electronic)
Cycloaddition Reactions in Organic Synthesis
Edited by
Shu Kobayashi and Karl Anker Jørgensen
Cycloaddition Reactions in Organic Synthesis.
Edited by S. Kobayashi and K. A. Jorgensen
Copyright © 2001 Wiley-VCH Verlag GmbH
ISBNs: 3-527-30159-3 (Hardcover); 3-527-60025-6 (Electronic)
Editors |
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This book was carefully produced. Nevertheless, |
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editors, authors and publisher do not warrant the |
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Kobayashi |
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information contained therein to be free of er- |
Shu |
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Graduate School of Pharmaceutical Sciences |
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rors. Readers are advised to keep in mind that |
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University of Tokyo |
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statements, data, illustrations, procedural details |
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The Hongo, Bunkyo-Ku |
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or other items may inadvertently be inaccurate. |
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113-0033 Tokyo |
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Japan |
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Karl Anker Jørgensen
Department of Chemistry
Aarhus University
Langelandsgade 140
8000 Aarhus C
Denmark
Cover
The sculpture is made by the Danish
glass artist Tchai Munch.
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© WILEY-VCH Verlag GmbH
Weinheim (Germany), 2002
All rights reserved (including those of translation in other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.
printed in the Federal Republic of Germany printed on acid-free paper
Typesetting K+V Fotosatz GmbH, Beerfelden Printing betz-druck GmbH, Darmstadt Bookbinding Wilhelm Osswald & Co., Neustadt
ISBN 3-527-30159-3
Cycloaddition Reactions in Organic Synthesis. V
Edited by S. Kobayashi and K. A. Jorgensen
Copyright © 2001 Wiley-VCH Verlag GmbH
ISBNs: 3-527-30159-3 (Hardcover); 3-527-60025-6 (Electronic)
Contents
List of Contributors XIII
Introduction 1
References 3
1 |
Catalytic Asymmetric Diels-Alder Reactions 5 |
|
Yujiro Hayashi |
1.1Introduction 5
1.2 |
The Chiral Lewis Acid-catalyzed Diels-Alder Reaction 6 |
1.2.1The Asymmetric Diels-Alder Reaction of , -Unsaturated Aldehydes
as Dienophiles 6
1.2.1.1Aluminum 6
1.2.1.2Boron 6
1.2.1.3Titanium 18
1.2.1.4Iron 20
1.2.1.5Ruthenium 21
1.2.1.6Chromium 21
1.2.1.7Copper 21
1.2.2The Asymmetric Diels-Alder Reaction of , -Unsaturated Esters as Dienophiles 23
1.2.3The Asymmetric Diels-Alder Reaction
of 3-Alkenoyl-1,3-oxazolidin-2-ones as Dienophiles 24
1.2.3.1Aluminum 26
1.2.3.2Magnesium 26
1.2.3.3Copper 27
1.2.3.4Iron 34
1.2.3.5Nickel 34
1.2.3.6Titanium 36
1.2.3.7Zirconium 40
1.2.3.8Lanthanides 40
1.2.4 |
The Asymmetric Diels-Alder Reaction of Other Dienophiles 43 |
1.3 |
The Asymmetric Catalytic Diels-Alder Reaction Catalyzed by Base 46 |
1.4 |
Conclusions 48 |
VI Contents
1.5Appendix 48 Acknowledgment 53
References 53
2Recent Advances in Palladium-catalyzed Cycloadditions
Involving Trimethylenemethane and its Analogs 57
Dominic M. T. Chan
2.1General Introduction 57
2.2 |
Mechanism for [3+2] Carbocyclic Cycloaddition 58 |
2.3 |
Dynamic Behavior of TMM-Pd Complexes 59 |
2.4 |
Application in Organic Synthesis 60 |
2.4.1General Comment 60
2.4.2[3+2] Cycloaddition: The Parent TMM
2.4.2.1 |
Recent Applications in Natural and Unnatural Product Synthesis 61 |
2.4.2.2 |
Novel Substrates for TMM Cycloaddition 61 |
2.4.3 |
[3+2] Cycloaddition: Substituted TMM 63 |
2.4.3.1Cyclopropyl-substituted TMM 63
2.4.3.2Phenylthio-TMM 64
2.4.4 |
[3+2] Cycloaddition: Intramolecular Versions 64 |
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2.4.4.1 |
Introduction and Substrate Synthesis |
64 |
2.4.4.2 |
Synthesis of Bicyclo[3.3.0]octyl Systems |
65 |
2.4.4.3 |
Synthesis of Bicyclo[4.3.0]nonyl Systems 66 |
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2.4.4.4 |
Synthesis of Bicyclo[5.3.0]decyl Systems |
67 |
2.4.5Carboxylative Cycloadditions 67
2.4.6Carbonyl Cycloadditions 71
2.4.6.1Addition to Aldehydes 71
2.4.6.2Addition to Ketones 72
2.4.7Imine Cycloadditions 73
2.4.8[4+3] Cycloadditions 76
2.4.9[6+3] Cycloadditions 80
2.4.10[3+3] Cycloaddition 82
2.5Conclusions 83
References 83
3Enantioselective [2+1] Cycloaddition: Cyclopropanation with Zinc Carbenoids 85
Scott E. Denmark and Gregory Beutner
3.1Introduction 85
3.2 |
The Simmons-Smith Cyclopropanation – Historical Background 87 |
3.3 |
Structure and Dynamic Behavior of Zinc Carbenoids 90 |
3.3.1 |
Formation and Analysis of Zinc Carbenoids 90 |
3.3.2 |
Studies on the Schlenk Equilibrium for Zinc Carbenoids 93 |
3.4Stereoselective Simmons-Smith Cyclopropanations 100
3.4.1Substrate-directed Reactions 100
3.4.2Auxiliary-directed Reactions 108
Contents VII
3.4.2.1Chiral Ketals 108
3.4.2.2Chiral Vinyl Ethers 111
3.4.3In-situ Chiral Modification 115
3.4.3.1Chirally Modified Reagents 115
3.4.3.2Chirally Modified Substrates 118
3.4.4Asymmetric Catalysis 121
3.4.4.1General Considerations 121
3.4.4.2Initial Discoveries 122
3.4.4.3 |
Defining the Role of Reaction Protocol 127 |
3.5 |
Simmons-Smith Cyclopropanations – Theoretical Investigations 140 |
3.6 |
Conclusions and Future Outlook 146 |
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References 147 |
4 |
Catalytic Enantioselective Cycloaddition Reactions |
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of Carbonyl Compounds 151 |
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Karl Anker Jørgensen |
4.1Introduction 151
4.2 |
Activation of Carbonyl Compounds by Chiral Lewis Acids 151 |
4.2.1The Basic Mechanisms of Cycloaddition Reactions
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of Carbonyl Compounds with Conjugated Dienes |
152 |
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4.3 |
Cycloaddition Reactions of Carbonyl Compounds |
156 |
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4.3.1 |
Reactions of Unactivated Aldehydes 156 |
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4.3.1.1 |
Chiral Aluminum and Boron Complexes |
156 |
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4.3.1.2 |
Chiral Transitionand Lanthanide-metal Complexes 160 |
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4.3.2 |
Reactions of Activated Aldehydes 164 |
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4.3.2.1 |
Chiral Aluminum and Boron Complexes |
164 |
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4.3.3Reactions of Ketones 174
4.3.4Inverse Electron-demand Reactions 178
4.4Summary 182 Acknowledgment 183
References 183
5 |
Catalytic Enantioselective Aza Diels-Alder Reactions 187 |
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Kobayashi |
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Shu |
5.1Introduction 187
5.2 |
Aza Diels-Alder Reactions of Azadienes 188 |
5.3 |
Aza Diels-Alder Reactions of Azadienophiles 191 |
5.4 |
A Switch of Enantiofacial Selectivity 195 |
5.5Chiral Catalyst Optimization 198
5.6 |
Aza Diels-Alder Reactions of -Imino Esters with Dienes 203 |
5.7 |
Aza Diels-Alder Reactions of 2-Azadienes 205 |
5.8Perspective 207 References 207
VIII |
Contents |
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6 |
Asymmetric Metal-catalyzed 1,3-Dipolar Cycloaddition Reactions 211 |
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Kurt Vesterager Gothelf |
6.1Introduction 211
6.2 |
Basic Aspects of Metal-catalyzed 1,3-Dipolar Cycloaddition Reactions 212 |
6.2.1The 1,3-Dipoles 212
6.2.2 |
Frontier Molecular Orbital Interactions 213 |
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6.2.3 |
The Selectivities of 1,3-Dipolar Cycloaddition Reactions 216 |
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6.3 |
Boron Catalysts for Reactions of Nitrones |
218 |
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6.4 |
Aluminum Catalysts for Reactions of Nitrones |
219 |
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6.5 |
Magnesium Catalysts for Reactions of Nitrones |
224 |
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6.6 |
Titanium Catalysts for Reactions of Nitrones and Diazoalkanes 226 |
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6.7 |
Nickel Catalysts for Reactions of Nitrones |
232 |
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6.8 |
Copper Catalysts for Reactions of Nitrones |
233 |
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6.9 |
Zinc Catalysts for Reactions of Nitrones and Nitrile Oxides 235 |
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6.10 |
Palladium Catalysts for Reactions of Nitrones |
237 |
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6.11 |
Lanthanide Catalysts for Reactions of Nitrones |
239 |
6.12Cobalt, Manganese, and Silver Catalysts for Reactions of Azomethine
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Ylides 240 |
6.13 |
Rhodium Catalysts for Reactions of Carbonyl Ylides 242 |
6.14Conclusion 244
Acknowledgment 245
References 245
7Aqua Complex Lewis Acid Catalysts
for Asymmetric 3+2 Cycloaddition Reactions 249
Shuji Kanemasa
7.1Introduction 249
7.2DBFOX/Ph-Transition Metal Complexes
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and Diels-Alder Reactions 250 |
7.2.1 |
Preparation and Structure of the Catalysts 250 |
7.2.2Diels-Alder Reactions 252
7.2.3 |
Structure of the Substrate Complexes 255 |
7.2.4 |
Tolerance of the Catalysts 259 |
7.2.5Nonlinear Effect 260
7.3 |
Nitrone and Nitronate Cycloadditions 268 |
7.3.1Nickel(II) Complex-catalyzed Reactions 268
7.3.2 |
Role of MS 4 Å 270 |
7.3.3Nitronate Cycloadditions 272
7.3.4 |
Reactions of Monodentate Dipolarophiles 274 |
7.3.5Transition Structures 276
7.4Diazo Cycloadditions 278
7.4.1 |
Screening of Lewis Acid Catalysts 279 |
7.4.2 |
Zinc Complex-catalyzed Asymmetric Reactions 281 |
7.4.3Transition Structures 283
7.5 Conjugate Additions 285
Contents IX
7.5.1Thiol Conjugate Additions 285
7.5.2Hydroxylamine Conjugate Additions 288
7.5.3 |
Michael Additions of Carbon Nucleophiles 291 |
7.6Conclusion 294
References 295
8 |
Theoretical Calculations of Metal-catalyzed Cycloaddition Reactions 301 |
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Karl Anker Jørgensen |
8.1Introduction 301
8.2Carbo-Diels-Alder Reactions 302
8.2.1Frontier-molecular-orbital Interactions
for Carbo-Diels-Alder Reactions 302
8.2.2Activation of the Dienophile by Lewis Acids, Interactions,
Reaction Course, and Transition-state Structures 303
8.3Hetero-Diels-Alder Reactions 314
8.3.1Frontier-molecular-orbital Interactions
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for Hetero-Diels-Alder Reactions 314 |
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8.3.2 |
Normal Electron-demand Hetero-Diels-Alder Reactions |
315 |
8.3.3 |
Inverse Electron-demand Hetero-Diels-Alder Reactions |
319 |
8.4 |
1,3-Dipolar Cycloaddition Reactions of Nitrones 321 |
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8.4.1Frontier-orbital Interactions for 1,3-Dipolar Cycloaddition Reactions of Nitrones 321
8.4.2Normal Electron-demand Reactions 322
8.4.3Inverse Electron-demand Reactions 323
8.5Summary 326 Acknowledgment 326 References 326
Index 329
Cycloaddition Reactions in Organic Synthesis. XI
Edited by S. Kobayashi and K. A. Jorgensen
Copyright © 2001 Wiley-VCH Verlag GmbH
ISBNs: 3-527-30159-3 (Hardcover); 3-527-60025-6 (Electronic)
List of Contributors
Gregory Beutner |
Kurt Vesterager Gothelf |
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Department of Chemistry |
Center for Metal Catalyzed Reactions |
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University of Illinois |
Department of Chemistry |
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245 Roger Adams Laboratory |
Aarhus University |
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PO Box 18 |
8000 Aarhus C |
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600 S. Mathews Avenue |
Denmark |
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Urbana, IL 61801 |
Karl Anker Jørgensen |
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USA |
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Center for Metal Catalyzed Reactions |
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Dominic M. T. Chan |
Department of Chemistry |
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DuPont Crop Protection |
Aarhus University |
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Stine-Haskell Research Center |
8000 Aarhus C |
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PO Box 30 |
Denmark |
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Newark, DE 19714 |
Email: |
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USA |
kaj@chem.au.dk |
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Email: |
Fax: +45-86-19-6188 |
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dominic.m.chan@usa.dupont.com |
Yujiro Hayashi |
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Fax: +01-302-366-5738 |
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Department of Industrial Chemistry |
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Scott E. Denmark |
Faculty of Engineering |
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245 Roger Adams Laboratory |
Science University of Tokyo |
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Department of Chemistry |
Kagurazaka 1–3, Shinjuku-ku |
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University of Illinois |
Tokyo 162-8601 |
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PO Box 18 |
Japan |
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600 S. Mathews Avenue |
Email: hayashi@ci.kagu.sut.ac.jp |
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Urbana, IL 61801 |
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USA |
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Email: sdenmark@uiuc.edu |
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Fax: +01-217-333-3984 |
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