The Mizoroki-Heck Reaction

Cover Page......Page 1
Title: The Mizoroki–Heck Reaction......Page 3
ISBN 0470033940......Page 4
1 Mechanisms of the Mizoroki–Heck Reaction......Page 5
2 Focus on Catalyst Development and Ligand Design......Page 6
5 Formation of Carbocycles......Page 7
7 Chelation-Controlled Mizoroki–Heck Reactions......Page 8
9 Oxidative Heck-Type Reactions (Fujiwara–Moritani Reactions)......Page 9
13 Desymmetrizing Heck Reactions......Page 10
16 The Asymmetric Intramolecular Mizoroki–Heck Reaction in Natural Product Total Synthesis......Page 11
Foreword......Page 13
Preface......Page 14
Contributors......Page 16
1.1 Introduction......Page 19
1.2 Mechanism of the Mizoroki–Heck Reaction when the Catalytic Precursor is Pd(OAc)2 in the Absence of Ligand......Page 23
1.3 Mechanism of the Mizoroki–Heck Reaction when the Catalytic Precursor is Pd(OAc)2 Associated with Monophosphine Ligands......Page 25
1.4 Mechanism of the Mizoroki–Heck Reaction when the Catalytic Precursor is Pd(OAc)2 Associated with Bisphosphine Ligands......Page 34
1.5 Mechanism of the Mizoroki–Heck Reaction when the Catalytic Precursor is a P,C-Palladacycle......Page 43
1.6 Mechanism of the Mizoroki–Heck Reaction when the Ligand is an N--Heterocyclic Carbene......Page 50
1.7 Mechanism of the Mizoroki–Heck Reaction when the Ligand is a Bulky and Electron-Rich Monophosphine......Page 55
1.8 Conclusion......Page 59
References......Page 60
2.1 Introduction......Page 69
2.2 General Considerations: Types of Catalytic System......Page 70
2.3 Four Types of Intermolecular Mizoroki–Heck Catalytic System......Page 84
2.4 Palladium Precatalysts in Type 1 and Type 2 Mizoroki–Heck Reactions......Page 99
References......Page 136
3.1 Introduction......Page 151
3.2 Mechanistic Aspects......Page 152
3.3 Electron-Rich Alkenes......Page 159
3.4 Allylic Alkenes......Page 165
3.5 Electron-Poor Alkenes......Page 171
References......Page 175
4.1 Introduction......Page 181
4.2 Oxidative Coupling of Arenes......Page 182
4.3 Mizoroki–Heck Reactions of Carboxylic Acid Derivatives......Page 189
4.4 Summary and Outlook......Page 194
References......Page 195
5.1 Introduction......Page 197
5.2 Formation of Carbocycles by 5-exo-trig Cyclization......Page 198
5.3 Formation of Carbocycles by 5-endo-trig Cyclization......Page 206
5.4 Formation of Carbocycles by 6-exo-trig Cyclization......Page 208
5.5 Formation of Carbocycles by 6-endo-trig (dig) Cyclization......Page 216
5.6 Formation of Carbocycles by 7-exo-trig (dig) Cyclization......Page 220
5.7 Formation of Carbocycles by 7-endo-trig Cyclization......Page 222
5.8 Formation of Eight-Membered and Larger Carbocycles......Page 223
References......Page 226
6.1 Introduction......Page 233
6.2 ‘Cyclic’ Peculiarities and Constraints......Page 234
6.3 Formation of Five-Membered Cycles......Page 238
6.4 Formation of Six-Membered Cycles......Page 253
6.5 Formation of Seven-Membered Cycles......Page 261
6.7 Formation of Macrocycles......Page 266
References......Page 268
7.1 Introduction......Page 277
7.2 Overview of Chelation-Controlled Mizoroki–Heck Reactions......Page 278
7.3 Allylic Alcohols and Related Systems......Page 280
7.4 Allylic Amines......Page 282
7.5 Vinyl Ethers......Page 283
7.6 Vinyl Silanes......Page 286
7.7 Vinyl Sul des......Page 287
7.8 Vinyl Sulfoxides......Page 288
7.9 Vinyl and Allylic Sulfones......Page 291
7.10 Other Chelation-Controlled Systems......Page 292
7.11 Summary......Page 294
References......Page 295
8.1 Introduction......Page 299
8.2 Domino Mizoroki–Heck Reactions......Page 302
8.3 Mizoroki–Heck/Cross-Coupling Reactions......Page 314
8.4 Mizoroki–Heck/Nucleophilic Substitution (Tsuji–Trost Reactions)......Page 318
8.5 Mizoroki–Heck/CO-Insertions......Page 320
8.6 Mizoroki–Heck/C H Activations......Page 321
8.7 Mizoroki–Heck/Pericyclic Transformations......Page 325
8.8 Mizoroki–Heck Reactions/Mixed Transformations......Page 328
8.9 Cross-Coupling/Mizoroki–Heck Reactions......Page 336
8.10 Allylic Substitution (Tsuji–Trost)/Mizoroki–Heck Reaction......Page 340
8.11 Other Palladium(0)-Catalysed Processes Involving a Mizoroki–Heck-Type Reaction......Page 342
8.12 Palladium(II)-Catalysed Transformations Involving a Mizoroki–Heck-Type Reaction......Page 345
References......Page 350
9.1 Introduction......Page 363
9.2 Intermolecular Fujiwara–Moritani Reactions via Electrophilic Palladation......Page 364
9.3 Intermolecular Fujiwara–Moritani Reactions via Directing Groups......Page 375
9.4 Intramolecular Fujiwara–Moritani Reactions......Page 378
References......Page 396
10.1 Introduction......Page 401
10.2 Copper-Catalysed Mizoroki–Heck-Type Reactions......Page 402
10.3 Nickel-Catalysed Mizoroki–Heck-Type Reactions......Page 404
10.4 Platinum-Catalysed Mizoroki–Heck-Type Reactions......Page 408
10.5 Cobalt-Catalysed Mizoroki–Heck-Type Reactions......Page 409
10.6 Rhodium-Catalysed Mizoroki–Heck-Type Reactions......Page 413
10.7 Iridium-Catalysed Mizoroki–Heck-Type Reactions......Page 414
10.8 Ruthenium-Catalysed Mizoroki–Heck-Type Reactions......Page 415
References......Page 418
11.2 Mechanism......Page 423
11.3 P,P Ligands and Derivatives......Page 425
11.4 P, N Ligands......Page 435
11.5 Other Ligand Classes......Page 445
References......Page 446
12.1 Introduction......Page 451
12.2 Mechanism......Page 453
12.3 Catalyst Systems......Page 463
12.4 Reaction Scope: 4-exo and 5-exo Enantioselective Cyclizations......Page 468
References......Page 476
13.1 Introduction......Page 481
13.2 Cyclic Dienes as Cyclization Precursors......Page 482
13.3 Bicyclic Diene as Cyclization Precursors......Page 491
13.4 Acyclic Dienes as Cyclization Precursors......Page 493
13.5 Desymmetrization of Leaving Groups......Page 495
References......Page 498
14.1 General Remarks......Page 503
14.2 The Mizoroki–Heck Reaction on Solid Supports......Page 504
14.3 Outlook and Conclusion......Page 508
References......Page 509
15.1 Introduction......Page 513
15.2 Solvent Systems......Page 514
15.3 Energy Input......Page 535
15.4 Additional Systems......Page 538
References......Page 539
16.1 Introduction......Page 551
16.2 General Features of the Asymmetric Intramolecular Mizoroki–Heck Reaction......Page 552
16.3 Natural Product Total Synthesis: Formation of Tertiary Stereocentres......Page 556
16.4 Natural Product Total Synthesis: Formation of Quaternary Stereocentres......Page 563
References......Page 580
A......Page 587
B......Page 590
C......Page 591
D......Page 593
E......Page 594
H......Page 595
I......Page 596
L......Page 597
M......Page 598
O......Page 599
P......Page 600
S......Page 602
T......Page 603
W......Page 604
X,Y......Page 605