Foreword ........................................................ V
Preface ...................................................... XIII
List of Contributors ........................................... XV
1 General Aspects and Historical Background .................... 1
Marco Bandini
1.1 Introduction ............................................ 1
1.2 General Aspects and Historical Background ............... 3
1.3 Catalytic Enantioselective FC Reactions: An
Introduction ............................................ 5
1.3.1 Alkylating Agents ................................ 6
1.3.2 Privileged Catalysts ............................. 9
1.3.3 Aromatic Compounds and Reaction Conditions ...... 13
References .................................................. 14
2 Michael Addition ............................................ 17
2.1 Chelating α, β-Unsaturated Compounds ................... 17
Jesus M. Garcia, Mikel Oiarbide and Claudio Palomo
2.1.1 Chelating Compounds ............................. 18
2.1.1.1 Alkylidene Malonates ................... 19
2.1.1.2 β, γ-Unsaturated α-Ketoesters .......... 25
2.1.1.3 α'-Hydroxy Enones ...................... 28
2.1.1.4 α'-Phosphonate Enones .................. 31
2.1.1.5 α, β-Unsaturated Acyl Compounds ........ 32
2.1.1.5.1 α, β-Unsaturated Acyl
Phosphonates ................ 32
2.1.1.5.2 α, β-Unsaturated 2-Acyl
Imidazoles .................. 34
2.1.1.6 α, β-Unsaturated Thioesters ............ 39
2.1.1.7 Nitroacrylates ......................... 40
2.1.1.8 Experimental: Selected Procedures ...... 42
2.2 Simple α, β-Unsaturated Substrates ..................... 49
Giuseppe Bartoli and Paolo Melchiorre
2.2.1 Introduction .................................... 49
2.2.1.1 α, β-Unsaturated Aldehydes ............. 50
2.2.1.1.1 Organocatalysis ............. 50
2.2.1.1.2 Organocatalytic Domino
Reactions ................... 55
2.2.1.1.3 Experimental: Selected
Procedures .................. 57
2.2.1.2 α, β-Unsaturated Ketones ............... 60
2.2.1.2.1 Organometallic Catalysis .... 60
2.2.1.2.2 Organocatalysis ............. 61
2.2.1.2.3 Experimental: Selected
Procedures .................. 64
2.2.2 Intramolecular Approach ......................... 65
2.3 Nitroalkenes ........................................... 67
Luca Bernardi and Alfredo Ricci
2.3.1 Introduction .................................... 68
2.3.2 Organocatalytic Enantioselective Reactions ...... 68
2.3.2.1 Friedel-Crafts Alkylation of Indoles ... 68
2.3.2.1.1 Thiourea Catalysts ......... 69
2.3.2.1.2 Bissulfonamide Catalysts ... 72
2.3.2.1.3 Phosphoric Acid
Catalysts .................. 73
2.3.2.1.4 Synthetic Applications ..... 74
2.3.3 Friedel-Crafts Reactions of Naphthols ........... 75
2.3.3.1 Thiourea Catalysts ..................... 75
2.3.4 Addition of 1,2,3-Triazoles ..................... 76
2.3.4.1 Cinchona Alkaloids Catalysts ........... 77
2.3.5 Conclusion and Outlook .......................... 78
2.3.6 Experimental: Selected Procedures ............... 79
2.3.7 Lewis Acid Catalyzed Enantioselective
Reactions ....................................... 80
2.3.7.1 Friedel-Crafts Reactions of Indoles .... 81
2.3.7.1.1 Zinc Catalysts .............. 81
2.3.7.1.2 Copper and Aluminum
Catalysts ................... 84
2.3.7.2 Friedel-Crafts Reactions of Furans
and Pyrroles ........................... 88
2.3.7.2.1 Zinc Catalysts .............. 88
2.3.7.3 Conclusion and Outlook ................. 90
2.3.7.4 Experimental: Selected Procedures ...... 91
References .................................................. 94
3 Addition to Carbonyl Compounds ............................. 101
3.1 Aldehydes/Ketones ..................................... 101
Jia-Rong Chen and Wen-Jing Xiao
3.1.1 Introduction ................................... 101
3.1.2 Organometallic Catalysis ....................... 102
3.1.2.1 Fundamental Examples and Mechanism .... 102
3.1.2.1.1 Chiral Titanium (IV)
Catalysis .................. 103
3.1.2.1.2 Chiral Bisoxazoline-
Cu(II) Catalysis ........... 108
3.1.2.2 Experiments: Selected Representative
Procedures ............................ 114
3.1.3 Organocatalysis ................................ 116
3.1.3.1 Fundamental Examples and Mechanism .... 116
3.1.3.2 Experiments: Selected Representative
Procedures ............................ 118
3.1.4 Heterogeneous Catalysis ........................ 118
3.2 Imines ................................................ 119
Shu-Li You
3.2.1 Catalytic Asymmetric Friedel-Crafts Reaction
of Imines ...................................... 120
3.2.1.1 Intermolecular Approach ............... 120
3.2.1.1.1 Organometallic Catalysis ... 120
3.2.1.1.2 Organocatalysis ............ 123
3.2.1.2 Pictet-Spengler Reaction .............. 132
3.2.2 Selected Procedures ............................ 138
References ................................................. 140
4 Nucleophilic Allylic Alkylation and Hydroarylation of
Allenes .................................................... 145
Marco Bandini and Achille Umani-Ronchi
4.1 Introduction .......................................... 145
4.2 Allylic Alkylations ................................... 147
4.2.1 Intermolecular Approach ........................ 147
4.2.1.1 Benzene-Like Compounds ................ 147
4.2.1.2 Indoles ............................... 150
4.2.1.3 Asymmetric Allylations ................ 152
4.2.1.4 Experimental: Selected Procedures ..... 155
4.2.2 Intramolecular Approaches ...................... 156
4.2.2.1 Introduction and Fundamental
Examples .............................. 156
4.2.2.2 Experimental: Selected Procedures ..... 159
4.3 Metallo-Catalyzed Hydroarylation of Allenes ........... 160
4.3.1 Introduction and Fundamental Examples .......... 160
4.3.2 Experimental: Selected Procedures .............. 163
References .................................................... 164
5 Nucleophilic Substitution on Csp3 Carbon Atoms ............. 167
Marco Bandini and Pier Giorgio Cozzi
5.1 Ring-Opening of Epoxides .............................. 168
5.1.1 Introduction ................................... 168
5.1.2 Enantiomerically Pure Epoxides ................. 169
5.1.2.1 Introduction .......................... 169
5.1.2.2 Indium(III) Catalysis ................. 172
5.1.2.3 Mechanism of Indium(III) Catalysis .... 175
5.1.2.4 Gold(III) Catalysis ................... 176
5.1.2.5 Mechanism of Gold(III) Catalysis ...... 177
5.1.2.6 Experiments: Selected Procedures ...... 177
5.1.3 Asymmetric Ring-Opening of Racemic and meso
Epoxides ....................................... 179
5.1.3.1 Introduction .......................... 179
5.1.3.2 Salen-Chromium-Catalyzed Kinetic
Resolution of Epoxides with Indoles ... 179
5.1.3.3 Experiments: Selected Procedures ...... 180
5.2 Direct Activation of Alcohols ......................... 181
5.2.1 Introduction ................................... 181
5.2.2 Diastereoselective Reactions ................... 182
5.2.2.1 BF3-Mediated Reactions ................ 183
5.2.2.2 Gold(III) Catalysis ................... 184
5.2.3 Enantioselective Reactions ..................... 187
5.2.3.1 Ruthenium Catalysis ................... 187
5.2.3.2 Brønsted Acid Catalysis ............... 191
5.2.3.3 Experiments: Selected Procedures ...... 192
5.2.3.4 FC Reactions with Chiral Ferrocenyl
Compounds ............................. 193
5.2.3.4.1 Indium-Promoted
Nucleophilic Substitution
with Ferrocene ............. 193
5.2.3.4.2 "On Water" FC Reactions .... 194
5.2.3.4.3 Experiments: Selected
Procedures ................. 196
References ................................................ 198
6 Unactivated Alkenes ........................................ 203
Ross A. Widenhoefer
6.1 Introduction .......................................... 203
6.2 Early Studies ......................................... 204
6.2.1 Enantioselective Hydroarylation of
Norbornene ..................................... 204
6.2.2 Atropselective Alkylation of Biaryls ........... 206
6.3 Rh(I)-Catalyzed Enantioselective Hydroarylation of
Iminoarenes ........................................... 207
6.3.1 Catalyst Control ............................... 207
6.3.1.1 Alkylation of Aromatic Ketimines ...... 207
6.3.1.2 Alkylation of Aromatic Aldimines ...... 209
6.3.2 Directing Group Control ........................ 211
6.3.2.1 Synthesis of (+)-Lithospermic Acid .... 211
6.3.2.2 Optimization and Scope ................ 213
6.4 Pt(II)-Catalyzed Enantioselective Hydroarylation of
Alkenylindoles ........................................ 214
6.5 Au(I)-Catalyzed Enantioselective Hydroarylation of
Allenylindoles ........................................ 217
6.6 Conclusions and Outlook ............................... 219
6.7 Experimental: Selected Procedures ..................... 220
References ................................................. 221
7 Catalytic Asymmetric Friedel-Crafts Alkylations in Total
Synthesis .................................................. 223
Conzalo Blay, José R. Pedro and Carlos Vila
7.1 Introduction .......................................... 223
7.2 Total Synthesis of Indole-Containing Compounds ........ 224
7.2.1 Synthesis of β-indolyl-Propanoic Acids ......... 224
7.2.2 Synthesis of Tryptamine and Tryptophan
Analogs ........................................ 225
7.2.3 Synthesis of Polycyclic Indoles ................ 228
7.2.4 Synthesis of 2-Aminomethyl Indoles ............. 229
7.2.5 Experiments: Selected Procedures ............... 232
7.3 Total Synthesis of Pyrrole-Containing Compounds ....... 240
7.3.1 Synthesis of (+)-Heliorridane .................. 240
7.3.2 Synthesis of the Indolizidine Alkaloids
Tashiromine, epi-Tashiromine, Razhinal,
Rhazinilam, Leuconolam and epi-Leuconalam ...... 241
7.3.3 Synthesis of Pyrrolo[1,2-a]pyrazines ........... 242
7.3.4 Experiments: Selected Procedures ............... 244
7.4 Friedel-Crafts Alkylation of Furan Derivatives in
Total Synthesis ....................................... 247
7.4.1 Synthesis of Aminobutenolides .................. 248
7.4.2 Experiments: Selected Procedures ............... 248
7.5 Friedel-Crafts Alkylation of Arenes in Total
Synthesis ............................................. 249
7.5.1 Synthesis of Optically Active Mandelic Acid
Derivatives and Aromatic α-Amino Acids ......... 250
7.5.2 Synthesis of Optically Active Chromanes ........ 250
7.5.3 Experiments: Selected Procedures ............... 251
7.6 Asymmetric Synthesis of Natural Products Based on
Diastereoselective Friedel-Crafts Reactions ........... 253
7.6.1 Synthesis of Hapalindole Alkaloids ............. 253
7.6.2 Synthesis of Acremoauxin A and Oxazinin 3 ...... 255
7.6.3 Synthesis of (S)-Ketoralac ..................... 256
7.6.4 Synthesis of (-)-Lintetralin ................... 257
7.6.5 Synthesis of (+)-Erogorgiaene .................. 258
7.6.6 Synthesis of (+)-Bruguierol С .................. 260
7.6.7 Synthesis of (-)-Talaumidin .................... 261
7.6.8 Experiments: Selected Procedures ............... 262
References .................................................... 268
8 Industrial Friedel-Crafts Chemistry ........................ 271
Duncan J. Macquarrie
8.1 Introduction .......................................... 271
8.2 Green Chemistry and the Friedel-Crafts Reaction ....... 272
8.2.1 Green Chemical Assessment of Friedel-Crafts
Processes ...................................... 272
8.3 Heterogeneous Catalysts for the Friedel-Crafts
Reaction .............................................. 275
8.3.1 Zeolites ....................................... 275
8.3.2 Clays and Other Solid Acids .................... 277
8.4 Large Scale Hydrocarbon Processing .................... 278
8.4.1 Ethylbenzene and Cumene ........................ 278
8.4.2 Linear Alkyl Benzenes .......................... 279
8.4.3 Dialkylated Biaryls ............................ 280
8.4.4 Alkylanilines and Related Compounds ............ 280
8.4.5 Alkylphenol Production ......................... 281
8.4.6 Diarylmethanes ................................. 282
8.4.7 Hydroxyalkylation of Aromatics ................. 282
8.4.8 Pechmann Syntheses ............................. 284
8.4.9 Use of Epoxides as Alkylating Agents ........... 284
8.5 Conclusions and Perspectives .......................... 286
References .................................................... 286
Index ......................................................... 289
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