Preface ............................................... XV
List of Contributors ................................. XIX
1 BINAP .................................................. 1
Takeshi Ohkuma and Nobuhito Kurono
1.1 Introduction: Structural Consideration ................. 1
1.2 Hydrogenation of Olefins ............................... 3
1.3 Hydrogenation of Ketones ............................... 6
1.3.1 Functionalized Ketones ................................. 6
1.3.2 Simple Ketones ......................................... 9
1.4 Isomerization of Allylamines and Allylalcohols ........ 13
1.5 Hydroboration, Hydrosilylation, Hydroacylation, and
Hydroamination ........................................ 14
1.6 Allylic Alkylation .................................... 18
1.7 Heck Reaction ......................................... 18
1.7.1 Intramolecular Reaction ............................... 18
1.7.2 Intermolecular Reaction ............................... 19
1.8 Aldol and Mannich-Type Reactions ...................... 21
1.8.1 Aldol Reaction ........................................ 21
1.8.2 Mannich-Type Reaction ................................. 23
1.9 Nucleophilic Additions to Carbonyl and Imino
Compounds ............................................. 24
1.9.1 Allylation ............................................ 24
1.9.2 Alkenylation and Arylation ............................ 25
1.9.3 Dienylation ........................................... 26
1.9.4 Cyanation ............................................. 27
1.10 α-Substitution Reactions of Carbonyl Compounds ........ 28
1.10.1 Fluorination and Amination ............................ 28
1.10.2 Arylation and Orthoester Alkylation ................... 29
1.11 Michael-Type Reactions ................................ 30
1.11.1 Michael Reaction ...................................... 30
1.11.2 Aza-Michael Reaction .................................. 32
1.12 Conjugate Additions Using Organoboron and Grignard
Reagents .............................................. 32
1.13 Diels-Alder Reaction .................................. 35
1.14 Ene Reaction .......................................... 38
1.15 Cyclization ........................................... 38
1.15.1 Intramolecular Reactions of Enynes .................... 38
1.15.2 [3+2] and [5+2] Cycloaddition Reactions ............... 39
1.15.3 [2+2+2] Cycloaddition Reactions ....................... 42
1.15.4 Pauson-Khand Type Reactions ........................... 43
1.16 Ring-Opening Reactions ................................ 45
1.17 Concluding Remarks .................................... 45
2 Bisphosphacycles - From DuPhos and BPE to a Diverse
Set of Broadly Applied Ligands ........................ 55
Weicheng Zhang and Xumu Zhang
2.1 Introduction .......................................... 55
2.2 Development of Bisphosphacycle Ligands ................ 55
2.2.1 Structural Features of DuPhos and BPE ................. 55
2.2.2 Strategies of Ligand Design ........................... 58
2.3 Applications of Bisphosphacycle Ligands ............... 65
2.3.1 Asymmetric Hydrogenation .............................. 65
2.3.2 Asymmetric Hydroformylation ........................... 75
2.3.3 Asymmetric Hydrosilylation ............................ 77
2.3.4 Asymmetric Hydroacylation ............................. 77
2.3.5 Asymmetric Cycloisomerization, Cycloaddition, and
Cyclization ........................................... 78
2.3.6 Asymmetric Phosphination .............................. 81
2.3.7 Asymmetric Nucleophilic Addition to Ketones and
Ketimines ............................................. 82
2.3.8 Asymmetric Conjugate Addition ......................... 85
2.3.9 Miscellaneous Reactions ............................... 85
2.4 Concluding Remarks .................................... 87
3 Josiphos Ligands: From Discovery to Technical
Applications .......................................... 93
Hans-Ulrich Blaser, Benoît Pugin, Felix Spindler,
Esteban Mejía, and Antonio Togni
3.1 Introduction and Background ........................... 93
3.2 Discovery and Development of the Josiphos Ligand
Family ................................................ 94
3.3 Why Are Josiphos Ligands So Effective? ................ 97
3.3.1 General Considerations ................................ 97
3.3.2 Structural Aspects of Transition Metal Complexes
Containing Josiphos and Josiphos-Like Ligands ......... 99
3.4 Catalytic Profile of the Josiphos Ligand Family ...... 104
3.4.1 Enantioselective Reductions of C=C, C=O and C=N
Bonds ................................................ 104
3.4.1.1 Enantioselective Hydrogenation of C=C Bonds .......... 104
3.4.1.2 Copper-Catalyzed Reduction of Activated C=C bonds
with PMHS (Conjugate Reduction) ...................... 110
3.4.1.3 Enantioselective Hydrogenation of C=O Bonds .......... 111
3.4.1.4 Enantioselective Hydrogenation of C=N Bonds .......... 114
3.4.2 Enantioselective Hydrofunctionalizations ............. 118
3.4.2.1 Hydroboration ........................................ 118
3.4.2.2 Hydroamination and Hydrophosphonation ................ 119
3.4.2.3 Hydrocarboxylation ................................... 120
3.4.3 Enantioselective C-C Bond Forming Reactions .......... 120
3.4.3.1 Allylic Alkylation ................................... 120
3.4.3.2 Michael Addition ..................................... 121
3.4.3.3 Heck Reaction ........................................ 122
3.4.3.4 Miscellaneous C-C Reactions .......................... 123
3.4.4 Miscellaneous Enantioselective Reactions ............. 125
3.4.4.1 Isomerization of Allylamines ......................... 125
3.4.4.2 Ring-Opening of Oxabicycles .......................... 125
3.4.4.3 Allylic Substitution ................................. 126
3.4.5 Application in Non-Enantioselective Reactions ........ 127
3.5 Concluding Remarks ................................... 127
4 Chiral Spiro Ligands ................................. 137
Shou-Fei Zhu and Qi-Lin Zhou
4.1 Introduction ......................................... 137
4.2 Preparation of Chiral Spiro Ligands .................. 139
4.3 Asymmetric Hydrogenation ............................. 144
4.3.1 Hydrogenation of Functionalized Olefins .............. 144
4.3.1.1 Hydrogenation of Enamides ............................ 144
4.3.1.2 Hydrogenation of Enamines ............................ 146
4.3.1.3 Hydrogenation of α,β-Unsaturated Acids ............... 146
4.3.2 Hydrogenation of Ketones and Aldehydes ............... 151
4.3.2.1 Hydrogenation of Simple Ketones ...................... 151
4.3.2.2 Hydrogenation of Racemic 2-Substituted Ketones via
DKR .................................................. 151
4.3.2.3 DKR Hydrogenation of Racemic 2-Substituted
Aldehydes ............................................ 153
4.3.3 Hydrogenation of Imines .............................. 154
4.3.4 Hydrogenation of 2-Substituted Quinolines ............ 154
4.4 Asymmetric Carbon-Carbon Bond Forming Reaction ....... 155
4.4.1 Rhodium-Catalyzed Arylation of Carbonyl Compounds
and Imines ........................................... 155
4.4.2 Palladium-Catalyzed Umpolung Allylation of
Aldehydes ............................................ 158
4.4.3 Copper-Catalyzed Conjugate Addition Reaction ......... 158
4.4.4 Copper-Catalyzed Ring-Opening Reaction with
Grignard Reagents .................................... 158
4.4.5 Nickel-Catalyzed Three-Component Coupling Reaction ... 159
4.4.6 Nickel-Catalyzed Hydrovinylation Reaction ............ 162
4.4.7 Rhodium-Catalyzed Hydrosilylation/Cyclization
Reaction ............................................. 167
4.4.8 Palladium-Catalyzed Asymmetric Oxidative
Cyclization .......................................... 162
4.4.9 Gold-Catalyzed Ring Expanding Cycloisomerization ..... 163
4.5 Asymmetric Carbon-Heteroatom Bond Forming Reaction ... 163
4.5.1 Palladium-Catalyzed Hydrosilylation .................. 163
4.5.2 Palladium-Catalyzed Wacker-Type Oxidative
Cyclization Reaction ................................. 163
4.5.3 Copper-Catalyzed Carbene Insertion into X-H Bonds .... 164
4.5.4 Allene-Based Allylic Cyclization Reactions ........... 166
4.6 Conclusion ........................................... 167
5 Chiral Bisoxazoline Ligands .......................... 171
Levi M. Stanley and Mukund P. Sibi
5.1 Introduction ......................................... 172
5.2 Enantioselective Carbon-Carbon Bond Formation ........ 176
5.2.1 Addition of Carbon Nucleophiles to C=O and C=N
Bonds ................................................ 176
5.2.1.1 Aldol Reactions ...................................... 176
5.2.1.2 Mannich-Type Reactions ............................... 177
5.2.1.3 Nitroaldol (Henry) Reactions ......................... 179
5.2.1.4 Nitro-Mannich (Aza-Henry) Reactions .................. 182
5.2.1.5 Addition of Activated Carbon Nucleophiles to
Carbonyl Electrophiles ............................... 182
5.2.1.6 Addition of Activated Carbon Nucleophiles to
Imines ............................................... 183
5.2.1.7 Ene Reactions ........................................ 184
5.2.1.8 Friedel-Crafts Reactions of Aromatic Compounds with
C=O and C=N Bonds .................................... 184
5.2.2 1,4-Addition of Carbon Nucleophiles to
α,β-Unsaturated Acceptors ............................ 186
5.2.3 Reactions of Radicals Alpha to Carbonyls ............. 190
5.2.4 Cyclization Reactions ................................ 191
5.2.5 Rearrangement Reactions .............................. 192
5.3 Enantioselective Carbon-Heteroatom Bond Formation .... 193
5.3.1 1,4-Addition of Heteroatom Nucleophiles to
α,β-Unsaturated Acceptors ............................ 193
5.3.1.1 1,4-Addition of Nitrogen Nucleophiles ................ 193
5.3.1.2 1,4-Addition of Sulfur and Oxygen Nucleophiles ....... 195
5.3.1.3 1,4-Addition of Boron Nucleophiles ................... 195
5.3.2 Allylic Functionalization Reactions .................. 196
5.3.3 α-Heteroatom Functionalization of Carbonyl
Compounds ............................................ 196
5.3.3.1 Amination ............................................ 196
5.3.3.2 Oxygenation .......................................... 197
5.3.3.3 Halogenation ......................................... 197
5.3.4 X-H Insertion Reactions (X=O,N,S) .................... 198
5.3.5 Cyclization Reactions ................................ 199
5.3.5.1 Carbonylative Cyclization ............................ 199
5.3.5.2 Wacker-Type Cyclizations ............................. 199
5.3.5.3 Hydroamination ....................................... 201
5.3.6 Kinetic Resolution and Desymmetrization Reactions .... 201
5.3.6.1 Kinetic Resolution ................................... 201
5.3.6.2 Desymmetrization ..................................... 201
5.4 Enantioselective Cycloaddition Reactions ............. 202
5.4.1 Carbo-Diels-Alder Cycloadditions ..................... 202
5.4.2 Hetero-Diels-Alder Cycloadditions .................... 204
5.4.3 Cyclopropanations .................................... 205
5.4.4 Aziridination ........................................ 208
5.4.5 1,3-Dipolar Cycloadditions ........................... 209
5.4.6 Additional Cycloaddition Reactions ................... 211
5.5 Conclusions .......................................... 212
6 PHOX Ligands ......................................... 221
Cory C. Bausch and Andreas Pfaltz
6.1 Introduction ......................................... 221
6.2 Synthesis of PHOX Ligands ............................ 222
6.3 Nucleophilic Allylic Substitution .................... 224
6.3.1 Palladium-Catalyzed Allylic Substitution ............. 224
6.3.2 Tungsten- and Iridium-Catalyzed Allylic
Substitution ......................................... 229
6.3.3 Allylic Substitution in Total Synthesis .............. 230
6.4 Decarboxylative Tsuji Allylations .................... 231
6.4.1 Method Development ................................... 231
6.4.2 Application to Fluorinated Derivatives ............... 234
6.4.3 Applications in Total Synthesis ...................... 235
6.5 Heck Reaction ........................................ 237
6.5.1 Intermolecular Heck Reaction ......................... 237
6.5.2 Intramolecular Heck Reaction ......................... 238
6.6 Hydrogenation ........................................ 240
6.6.1 Hydrogenation of Imines .............................. 240
6.6.2 Hydrogenation of Trisubstituted Olefins .............. 240
6.6.3 Hydrogenation of Tetrasubstituted Olefins ............ 243
6.6.4 Hydrogenation of Vinyl Phosphonates .................. 243
6.6.5 Hydrogenation of α,β-Unsaturated Ketones ............. 244
6.6.6 Hydrogenation of Ketones ............................. 244
6.6.7 Transfer Hydrogenation of Ketones .................... 246
6.7 Cycloadditions ....................................... 246
6.7.1 [3+2] Cycloadditions ................................. 246
6.7.2 Diels-Alder Reactions ................................ 247
6.8 Miscellaneous Reactions .............................. 248
6.8.1 Hydros ilylations .................................... 248
6.8.2 Pauson-Khand Reaction ................................ 248
6.8.3 Decarboxylase Protonation ............................ 249
6.8.4 Sigmatropic Rearrangements ........................... 250
6.8.5 Desymmetrization Reactions ........................... 251
6.8.6 Asymmetric Arylations ................................ 253
6.9 Conclusion ........................................... 253
7 Chiral Salen Complexes ............................... 257
Wen-Zhen Zhang and Xiao-Bing Lu
7.1 Introduction ......................................... 257
7.2 Synthesis of Chiral Salen Complexes .................. 257
7.3 Structural Properties of Chiral Salen Complexes ...... 259
7.4 Asymmetric Reactions Catalyzed by Chiral Salen
Complexes ............................................ 262
7.4.1 Asymmetric Epoxidation ............................... 262
7.4.2 Asymmetric Ring-Opening of Epoxides .................. 266
7.4.2.1 Desymmetrization of Meso-Epoxides .................... 266
7.4.2.2 Kinetic Resolution of Racemic Epoxides ............... 269
7.4.2.3 Enantioselective Addition of Carbon Dioxide to
Propylene Oxide ...................................... 271
7.4.2.4 Asymmetric Alternating Copolymerization of Racemic
Epoxides and Carbon Dioxide .......................... 272
7.4.2.5 Enantioselective Homopolymerization of Epoxides ...... 273
7.4.3 Asymmetric Cyclopropanation .......................... 274
7.4.4 Asymmetric Conjugate Addition Reaction ............... 277
7.4.5 Asymmetric Diels-Alder Reaction ...................... 281
7.4.6 Asymmetric Cyanohydrin Synthesis ..................... 284
7.4.7 Miscellaneous Reactions .............................. 287
7.5 Conclusion and Outlook ............................... 289
8 BINOL ................................................ 295
Masakatsu Shibasaki and Shigeki Matsunaga
8.1 Introduction ......................................... 295
8.2 Applications in Reduction and Oxidation .............. 296
8.3 Metal/BINOL Chiral Lewis Acid Catalysts in
Asymmetric C-C Bond Forming Reactions ................ 300
8.3.1 Group IV Metal/BINOL Lewis Acid Catalysts ............ 300
8.3.2 Group XIII Metal/BINOL Lewis Acid Catalysts .......... 304
8.3.3 Rare Earth Metal/BINOL Lewis Acid Catalysts .......... 307
8.4 Acid/Base Bifunctional Metal/BINOL Catalysts ......... 308
8.4.1 Rare Earth Metal/Alkali Metal/BINOL Catalysts ........ 308
8.4.2 Group XIII Metal/Alkali Metal/BINOL Catalysts ........ 312
8.4.3 Other Metal/BINOL Complexes as Acid/Base
Bifunctional Catalysts ............................... 316
8.4.4 Lewis Acid/Lewis Base Bifunctional
Aluminium-Catalyst ................................... 321
8.5 BINOL in Organocatalysis ............................. 324
8.6 Summary .............................................. 329
9 TADDOLate Ligands .................................... 333
Hélène Pellissier
9.1 Introduction ......................................... 333
9.2 Nucleophilic Additions to C=O Double Bonds ........... 334
9.2.1 Organozinc Additions to Aldehydes .................... 334
9.2.2 Allylations .......................................... 335
9.2.3 Aldol-Type Reactions ................................. 336
9.2.4 Miscellaneous Reactions .............................. 338
9.3 Nucleophilic Conjugate Additions to
Electron-Deficient C=C Double Bonds .................. 339
9.4 Nucleophilic Substitutions ........................... 342
9.4.1 Allylic Substitutions ................................ 342
9.4.2 α-Halogenations of Carbonyl Compounds ................ 344
9.4.3 Miscellaneous Substitutions .......................... 345
9.5 Cycloaddition Reactions .............................. 345
9.5.1 Diels—Alder reactions ................................ 346
9.5.2 Hetero-Diels-Alder Reactions ......................... 347
9.5.3 Miscellaneous Cycloadditions ......................... 348
9.6 Oxidation and Reduction Reactions .................... 349
9.7 Miscellaneous Reactions .............................. 351
9.8 Conclusions .......................................... 354
10 Cinchona Alkaloids ................................... 361
Hongming Li, Yonggang Chen and Deng Li
10.1 Introduction ......................................... 361
10.2 Metal Catalysis ...................................... 363
10.3 Phase-Transfer Catalysis ............................. 367
10.3.1 Asymmetric Alkylations ............................... 367
10.3.2 Asymmetric Conjugate Additions ....................... 368
10.3.3 Asymmetric Aldol Reactions ........................... 368
10.3.4 Examples of Recent Applications ...................... 369
10.4 Nucleophilic Catalysis ............................... 370
10.4.1 Asymmetric Reactions with Ketenes .................... 370
10.4.2 Asymmetric Morita-Baylis-Hillman Reactions ........... 373
10.4.3 Asymmetric Cyanation of Simple Ketones ............... 374
10.4.4 Recent Applications of Nucleophilic Catalysis by
Cinchona Alkaloids ................................... 375
10.4.4.1 Asymmetric Conjugate Additions ....................... 375
10.4.4.2 Asymmetric Electrophilic Halogenations of Olefins .... 376
10.5 Base Catalysis ....................................... 377
10.5.1 Asymmetric Alcoholysis of Cyclic Anhydrides .......... 377
10.5.2 Conjugate Additions .................................. 380
10.5.3 Asymmetric Mannich and Aldol Reactions ............... 381
10.6 Cooperative and Multifunctional Catalysis ............ 382
10.6.1 Acid-Base Cooperative Catalysis ...................... 382
10.6.1.1 Asymmetric Conjugate Additions ....................... 382
10.6.1.2 Asymmetric 1,2-Additions to Carbonyls ................ 386
10.6.1.3 Asymmetric 1,2-Additions to lmines ................... 390
10.6.1.4 Asymmetric Friedel-Crafts Reactions .................. 391
10.6.1.5 Asymmetric Diels-Alder Reactions ..................... 393
10.6.1.6 Asymmetric Fragmentation ............................. 394
10.6.2 Base-lminium Cooperative Catalysis ................... 396
10.6.2.1 Asymmetric Conjugate Additions ....................... 396
10.6.2.2 Asymmetric Fridel-Crafts Additions ................... 398
10.6.2.3 Asymmetric Diels-Alder Reactions ..................... 399
10.6.2.4 Semipinacol-Type 1,2-Carbon Migration ................ 399
10.6.3 Multifunctional Cooperative Catalysis ................ 400
10.6.3.1 Tandem Conjugate Addition-Protonation Reactions ...... 400
10.6.3.2 Catalytic Asymmetric Peroxidations ................... 400
10.7 Conclusion ........................................... 404
11 Proline Derivatives .................................. 409
Shilei Zhang and Wei Wang
11.1 Introduction ......................................... 409
11.2 Proline as Organocatalyst ............................ 410
11.2.1 Aldol Reactions ...................................... 410
11.2.1.1 Intermolecular Aldol Reactions ....................... 410
11.2.1.2 Intramolecular Aldol Reactions ....................... 412
11.2.1.3 Synthesis of Carbohydrates by Proline-Catalyzed
Aldol Reactions ...................................... 413
11.2.2 Mannich Reactions Catalyzed by Proline ............... 414
11.2.3 Michael Addition Reactions Catalyzed by Proline ...... 415
11.2.4 Morita-Baylis-Hillman (MBH) Reactions Catalyzed by
Proline .............................................. 426
11.2.5 α-Amination, α-Aminoxylation, and α-Alkylation of
Carbonyl Compounds Catalyzed by Proline .............. 427
11.2.6 Cascade/One-Pot Reactions Catalyzed by Proline ....... 418
11.3 Proline Analogs as Organocatalysts ................... 419
11.3.1 4-Hydroxyproline as Organocatalyst ................... 419
11.3.2 Other Proline Analogs as Organocatalysts ............. 421
11.4 5-Pyrrolidin-2-yltetrazole as Organocatalyst ......... 422
11.5 Pyrrolidine-Based Sulfonamides as Organocatalysts .... 424
11.6 Pyrrolidine-Based Amides as Organocatalysts .......... 425
11.7 Pyrrolidine Diamine Catalysts ........................ 427
11.8 Diarylprolinols or Diarylprolinol Ether Catalysts .... 429
11.8.1 Aldol Reactions, Mannich Reactions, and Other
α-Functionalizations of Aldehydes Catalyzed by
Diarylprolinols or Diarylprolinol Silyl Ethers ....... 429
11.8.2 Michael Addition Reactions Catalyzed by
Diarylprolinols or Diarylprolinol Silyl Ethers ....... 430
11.8.2.1 Michael Additions through an Enamine Pathway ......... 430
11.8.2.2 Michael Additions through an Iminium Mechanism ....... 430
11.8.3 Cycloaddition Reactions Catalyzed by
Diarylprolinols or Diarylprolinol Silyl Ethers ....... 433
11.8.4 Cascade Reactions Catalyzed by Diarylprolinol Silyl
Ethers ............................................... 435
11.8.4.1 Three-Membered Rings Formed by a [1+2] Strategy ...... 435
11.8.4.2 Five-Membered Rings Formed by a [3+2] Strategy ....... 436
11.8.4.3 Six-Membered Rings Formed by a [4+2] Strategy ........ 437
11.8.4.4 Six-Membered Rings Formed by a [3+3] Strategy ........ 437
11.8.4.5 Six-Membered Rings Formed by a [2+2+2] Strategy ...... 438
11.8.4.6 Other Cascade Reactions 439
11.9 Concluding Remarks ................................... 439
Index ................................................ 447
|
