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Cycloaddition Reactions in Synthesis By Wiley
Contents
List of Contributors XIII
Introduction 1
References 3
1 Catalytic Asymmetric Diels-Alder Reactions 5
Yujiro Hayashi
1.1 Introduction 5
1.2 The Chiral Lewis Acid-catalyzed Diels-Alder Reaction 6
1.2.1 The Asymmetric Diels-Alder Reaction of , -Unsaturated Aldehydes
as Dienophiles 6
1.2.1.1 Aluminum 6
1.2.1.2 Boron 6
1.2.1.3 Titanium 18
1.2.1.4 Iron 20
1.2.1.5 Ruthenium 21
1.2.1.6 Chromium 21
1.2.1.7 Copper 21
1.2.2 The Asymmetric Diels-Alder Reaction of , -Unsaturated Esters
as Dienophiles 23
1.2.3 The Asymmetric Diels-Alder Reaction
of 3-Alkenoyl-1,3-oxazolidin-2-ones as Dienophiles 24
1.2.3.1 Aluminum 26
1.2.3.2 Magnesium 26
1.2.3.3 Copper 27
1.2.3.4 Iron 34
1.2.3.5 Nickel 34
1.2.3.6 Titanium 36
1.2.3.7 Zirconium 40
1.2.3.8 Lanthanides 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
1.5 Appendix 48
Acknowledgment 53
References 53
2 Recent Advances in Palladium-catalyzed Cycloadditions
Involving Trimethylenemethane and its Analogs 57
Dominic M.T. Chan
2.1 General 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
2.4.1 General 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
2.4.3.1 Cyclopropyl-substituted TMM 63
2.4.3.2 Phenylthio-TMM 64
2.4.4 [3+2] Cycloaddition: Intramolecular Versions 64
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
2.4.4.4 Synthesis of Bicyclo[5.3.0]decyl Systems 67
2.4.5 Carboxylative Cycloadditions 67
2.4.6 Carbonyl Cycloadditions 71
2.4.6.1 Addition to Aldehydes 71
2.4.6.2 Addition to Ketones 72
2.4.7 Imine Cycloadditions 73
2.4.8 [4+3] Cycloadditions 76
2.4.9 [6+3] Cycloadditions 80
2.4.10 [3+3] Cycloaddition 82
2.5 Conclusions 83
References 83
3 Enantioselective [2+1] Cycloaddition: Cyclopropanation
with Zinc Carbenoids 85
Scott E. Denmark and Gregory Beutner
3.1 Introduction 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
3.4 Stereoselective Simmons-Smith Cyclopropanations 100
3.4.1 Substrate-directed Reactions 100
3.4.2 Auxiliary-directed Reactions 108
VI Contents
3.4.2.1 Chiral Ketals 108
3.4.2.2 Chiral Vinyl Ethers 111
3.4.3 In-situ Chiral Modification 115
3.4.3.1 Chirally Modified Reagents 115
3.4.3.2 Chirally Modified Substrates 118
3.4.4 Asymmetric Catalysis 121
3.4.4.1 General Considerations 121
3.4.4.2 Initial 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
References 147
4 Catalytic Enantioselective Cycloaddition Reactions
of Carbonyl Compounds 151
Karl Anker Jørgensen
4.1 Introduction 151
4.2 Activation of Carbonyl Compounds by Chiral Lewis Acids 151
4.2.1 The Basic Mechanisms of Cycloaddition Reactions
of Carbonyl Compounds with Conjugated Dienes 152
4.3 Cycloaddition Reactions of Carbonyl Compounds 156
4.3.1 Reactions of Unactivated Aldehydes 156
4.3.1.1 Chiral Aluminum and Boron Complexes 156
4.3.1.2 Chiral Transition- and Lanthanide-metal Complexes 160
4.3.2 Reactions of Activated Aldehydes 164
4.3.2.1 Chiral Aluminum and Boron Complexes 164
4.3.3 Reactions of Ketones 174
4.3.4 Inverse Electron-demand Reactions 178
4.4 Summary 182
Acknowledgment 183
References 183
5 Catalytic Enantioselective Aza Diels-Alder Reactions 187
Shu Kobayashi
5.1 Introduction 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
5.5 Chiral 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
5.8 Perspective 207
References 207
Contents VII
6 Asymmetric Metal-catalyzed 1,3-Dipolar Cycloaddition Reactions 211
Kurt Vesterager Gothelf
6.1 Introduction 211
6.2 Basic Aspects ofMetal-catalyzed 1,3-DipolarCycloaddition Reactions 212
6.2.1 The 1,3-Dipoles 212
6.2.2 Frontier Molecular Orbital Interactions 213
6.2.3 The Selectivities of 1,3-Dipolar Cycloaddition Reactions 216
6.3 Boron Catalysts for Reactions of Nitrones 218
6.4 Aluminum Catalysts for Reactions of Nitrones 219
6.5 Magnesium Catalysts for Reactions of Nitrones 224
6.6 Titanium Catalysts for Reactions of Nitrones and Diazoalkanes 226
6.7 Nickel Catalysts for Reactions of Nitrones 232
6.8 Copper Catalysts for Reactions of Nitrones 233
6.9 Zinc Catalysts for Reactions of Nitrones and Nitrile Oxides 235
6.10 Palladium Catalysts for Reactions of Nitrones 237
6.11 Lanthanide Catalysts for Reactions of Nitrones 239
6.12 Cobalt, Manganese, and Silver Catalysts for Reactions of Azomethine
Ylides 240
6.13 Rhodium Catalysts for Reactions of Carbonyl Ylides 242
6.14 Conclusion 244
Acknowledgment 245
References 245
7 Aqua Complex Lewis Acid Catalysts
for Asymmetric 3+2 Cycloaddition Reactions 249
Shuji Kanemasa
7.1 Introduction 249
7.2 DBFOX/Ph-Transition Metal Complexes
and Diels-Alder Reactions 250
7.2.1 Preparation and Structure of the Catalysts 250
7.2.2 Diels-Alder Reactions 252
7.2.3 Structure of the Substrate Complexes 255
7.2.4 Tolerance of the Catalysts 259
7.2.5 Nonlinear Effect 260
7.3 Nitrone and Nitronate Cycloadditions 268
7.3.1 Nickel(II) Complex-catalyzed Reactions 268
7.3.2 Role of MS 4 Å 270
7.3.3 Nitronate Cycloadditions 272
7.3.4 Reactions of Monodentate Dipolarophiles 274
7.3.5 Transition Structures 276
7.4 Diazo Cycloadditions 278
7.4.1 Screening of Lewis Acid Catalysts 279
7.4.2 Zinc Complex-catalyzed Asymmetric Reactions 281
7.4.3 Transition Structures 283
7.5 Conjugate Additions 285
VIII Contents
7.5.1 Thiol Conjugate Additions 285
7.5.2 Hydroxylamine Conjugate Additions 288
7.5.3 Michael Additions of Carbon Nucleophiles 291
7.6 Conclusion 294
References 295
8 Theoretical Calculations of Metal-catalyzed Cycloaddition Reactions 301
Karl Anker Jørgensen
8.1 Introduction 301
8.2 Carbo-Diels-Alder Reactions 302
8.2.1 Frontier-molecular-orbital Interactions
for Carbo-Diels-Alder Reactions 302
8.2.2 Activation of the Dienophile by Lewis Acids, Interactions,
Reaction Course, and Transition-state Structures 303
8.3 Hetero-Diels-Alder Reactions 314
8.3.1 Frontier-molecular-orbital Interactions
for Hetero-Diels-Alder Reactions 314
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
8.4.1 Frontier-orbital Interactions for 1,3-Dipolar Cycloaddition Reactions
of Nitrones 321
8.4.2 Normal Electron-demand Reactions 322
8.4.3 Inverse Electron-demand Reactions 323
8.5 Summary 326
Acknowledgment 326
References 326
Index 329
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