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Contents  
 
Preface XV
List of Authors XVII
Volume 1 1
1 Introduction
Paul Knochel and Felix Kopp 		1
2 Polyfunctional Lithium Organometallics for Organic Synthesis
Miguel Yus and Francisco Foubelo 		7
2.1 Introduction 7
2.2 -Functionalized Organolithium Compounds 8
2.2.1 sp3-Hybridized –Oxygenated Organolithium Compounds 8
2.2.2 sp2-Hybridized -Oxygenated Organolithium Compounds 13
2.2.3 sp3-Hybridized -Nitrogenated Organolithium Compounds 14
2.2.4 sp2-Hybridized -Nitrogenated Organolithium Compounds 16
2.2.5 Other sp2-Hybridized -Functionalized Organolithium Compounds 18
2.3 -Functionalized Organolithium Compounds 18
2.3.1 sp3-Hybridized -Functionalized Organolithium Compounds 19
2.3.2 sp2-Hybridized -Functionalized Organolithium Compounds 22
2.4 -Functionalized Organolithium Compounds 24
2.4.1 -Functionalized Alkyllithium Compounds 24
2.4.2 -Functionalized Allyllithium Compounds 26
2.4.3 -Functionalized Benzyllithium Compounds 27
2.4.4 -Functionalized Akenyllithium Compounds 28
2.4.5 -Functionalized Alkynyllithium Compounds 30
2.5 -Functionalized Organolithium Compounds 31
2.5.1 -Functionalized Alkyllithium Compounds 31
2.5.2 -Functionalized Allyl and Benzyllithium Compounds 32
2.5.3 -Functionalized Alkenyllihium Compounds 33
2.5.4 -Functionalized Alkynyllithium Compounds 34
2.6 Remote Functionalized Organolithium Compounds 34
2.6.1 Remote Functionalized Alkyllithium Compounds 34
2.6.2 Remote Allyl and Benzyllithium Compounds 35
2.6.3 Remote Functionalized Alkenyl- and Alkynyllithium Compounds 36
3 Functionalized Organoborane Derivatives in Organic Synthesis
Paul Knochel, Hiriyakkanavar Ila, Tobias J. Korn, and Oliver Baron 		45
3.1 Introduction 45
3.2 Preparation and Reaction of Functionalized Aryl and Heteroaryl Boranes 45
3.2.1 Preparation from Polar Organometallics 45
3.2.2 Preparation from Aryl Halides and Sulfonates by Cross-coupling 50
3.2.3 Synthesis of Functionalized Aryl Boranes by Catalytic Aromatic C–H Borylation 54
3.2.4 Synthesis of Functionalized Trifluoroborates and their Palladium-catalyzed Suzuki–Miyaura Cross-coupling Reactions 57
3.2.5 Palladium-catalyzed Suzuki–Miyaura Cross-coupling Reactions of Functionalized Aryl and Heteroaryl Boronic Esters 58
3.2.6 Copper-mediated Carbon–Heteroatom-Bond-forming Reactions with Functionalized Aryl Boronic Acids 68
3.2.7 Palladium-catalyzed Acylation of Functionalized Aryl Boronic Acids 73
3.2.8 Miscellaneous C–C-bond Formations of Functionalized Aryl Organoboranes 74
3.2.9 Miscellaneous Reactions of Functionalized Alkenyl Boronic Acids 78
3.3 Preparation and Reactions of Functionalized Alkenyl Boranes 79
3.3.1 Synthesis of Alkenyl Boronic Acids by Transmetallation of Alkenyl Grignard Reagents with Boronate Esters 79
3.3.2 Synthesis of Functionalized Alkenyl Boronic Acids by Hydroboration of Functionalized Alkynes and their Suzuki Cross-coupling Reactions 79
3.3.3 Synthesis of Functionalized Alkenyl Boronic Esters by Cross-metathesis 81
3.3.4 Synthesis and Palladium-catalyzed Cross-coupling Reactions of Functionalized Alkenyl Trifluoroborates 82
3.3.5 Palladium-catalyzed Cross-coupling of Functionalized Alkenyl Boronates with Cyclopropyl Iodides 83
3.3.6 Intermolecular Suzuki Cross-coupling Reactions of Functionalized Alkenylborane Derivates: Application in Natural Product Synthesis (Alkenyl B-Alkenyl Coupling) 83
3.3.7 Intramolecular Macrocyclization via Suzuki Cross-coupling of Functionalized Alkenyl Boronic Esters (Alkenyl B-Alkenyl Coupling) 84
3.3.8 Three-component Mannich Reaction of Functionalized Alkenyl Boronic Acids (Petasis Reaction): Synthesis of , -Unsaturated -Amino Acids 85
3.3.9 Oxidation of Functionalized Alkenyl Boronic Esters to Aldehydes with Trimethylamine Oxide 86
3.3.10 Lewis-acid-catalyzed Nucleophilic Addition of Functionalized Alkenyl Boronic Esters to Activated N-acyliminium Ions 86
3.4 Preparation and Reactions of Functionalized Alkynlboron Derivatives 87
3.5 Synthesis and Reactions of Functionalized Allylic Boronates 88
3.6 Synthesis and Reactions of Functionalized Cyclopropyl Boronic Esters 90
3.7 Synthesis and Reactions of Functionalized Alkyl Boron Derivates 91
3.7.1 Synthesis of Aminoalkyl Boranes by Hydroboration and their Suzuki Cross-coupling Reaction 91
3.7.2 Synthesis of Functionalized Alkyl Boronates by Nucleophilic 1,4-Conjugate Addition of Borylcopper Species to , -Unsaturated Carbonyl Compounds 92
3.7.3 Preparation and B-alkyl-Suzuki–Miyaura Cross-coupling Reactions of Functionalized Alkyl Trifluoroborates 93
3.7.4 Silver(I)-promoted Suzuki Cross-coupling of Functionalized n-Alkyl Boronic Acids 94
3.7.5 Alkyl-Alkyl Suzuki Cross-coupling of Functionalized Alkyl Boranes with Alkyl Bromides, Chlorides and Tosylates 95
3.7.6 Synthesis of Natural and Unnatural Amino Acids via B-alkyl Suzuki Coupling of Functionalized Alkyl Boranes 95
3.7.7 Application of Intermolecular B-alkyl Suzuki Cross-coupling of Functionalized Alkyl Boranes in Natural Product Synthesis 96
3.8 Conclusion 104
4 Polyfunctional Magnesium Organometallics for Organic Synthesis
Paul Knochel, Arkady Krasovskiy, and Ioannis Sapountzis 		109
4.1 Introduction 109
4.2 Methods of Preparation of Grignard Reagents and their Uncatalyzed Reactions 110
4.2.1 Direct Oxidative Addition of Magnesium to Organic Halides 110
4.2.2 Metalation Reactions with Magnesium Amides 111
4.2.3 The Halogen–Magnesium Exchange Reaction 113
4.2.3.1 Early Studies 113
4.2.3.2 The Preparation of Functionalized Arylmagnesium Reagents 115
4.2.3.3 Halogen–Magnesium Exchange Using Lithium Trialkylmagnesiates 128
4.2.3.4 The Preparation of Functionalized Heteroarylmagnesium Reagents 129
4.2.4 The Preparation of Functionalized Alkenylmagnesium Reagents 136
4.2.5 Preparation of Functionalized Alkylmagnesium Reagents 142
4.2.6 Preparation of Functionalized Alkylmagnesium Carbenoids 143
4.3 Further Applications of Functionalized Grignard Reagents 146
4.4 Application of Functionalized Magnesium Reagents in Cross-coupling Reactions 155
4.4.1 Palladium-catalyzed Cross-coupling Reactions 155
4.4.2 Nickel-catalyzed Cross-coupling Reactions 157
4.4.3 Iron-catalyzed Cross-coupling Reactions 159
4.5 Summary and Outlook 164
5 Polyfunctional Silicon Organometallics for Organic Synthesis
Masaki Shimizu and Tamejiro Hiyama 		173
5.1 Introduction 173
5.2 Allylic Silanes 174
5.2.1 Intermolecular Reactions of Polyfunctional Allylic Silanes 174
5.2.2 Intramolecular Reactions of Polyfunctional Allylic Silanes 176
5.2.3 Tandem Reactions of Polyfunctional Allylic Silanes 180
5.2.4 Sequential Synthetic Reactions of Metal-containing Allylic Silanes 183
5.3 Alkenylsilanes 189
5.3.1 Intermolecular Reactions of Polyfunctional Alkenylsilanes 189
5.3.2 Intramolecular Reactions of Polyfunctional Alkenylsilanes 190
5.3.3 Synthetic Reactions of Metal-containing Alkenylsilanes 191
5.4 Alkylsilanes 193
5.4.1 Synthetic Reactions of Polyhalomethylsilanes 193
5.4.2 Synthetic Reactions of Cyclopropyl, Oxiranyl, and Aziridinylsilanes 195
5.4.3 Synthetic Reactions of Polysilylmethanes 196
5.5 Miscellaneous Preparations and Reactions of Polyfunctional Organosilicon Reagents 197
6 Polyfunctional Tin Organometallics for Organic Synthesis
Eric Fouquet and Agnès Herve 		203
6.1 Introduction 203
6.2 Metal-Catalyzed Coupling Reactions 203
6.2.1 The Stille Cross-Coupling Reaction 203
6.2.1.1 Mechanism 204
6.2.1.2 Organotins for the Stille Reaction 205
6.2.1.3 Substrates 208
6.2.1.4 Intermolecular Stille Cross-coupling 210
6.2.1.5 Intramolecular Stille Cross-coupling 212
6.2.1.6 Solid-Phase-Supported Stille Coupling 214
6.2.1.7 Stille Coupling Catalytic in Tin 215
6.2.2 Other Metal-Catalyzed Coupling Reactions 215
6.2.2.1 Palladium-Catalyzed Reactions 215
6.2.2.2 Copper-Catalyzed Reactions 215
6.2.2.3 Nickel-Catalyzed Reactions 216
6.2.2.4 Rhodium-Catalyzed Reactions 216
6.3 Nucleophilic Additions 217
6.3.1 Nucleophilic Addition onto Carbonyl Compounds 217
6.3.1.1 Introduction 217
6.3.1.2 Functionalized Allyltins 217
6.3.1.3 Catalytic Use of Lewis Acid 221
6.3.1.4 Enantioselectivity 221
6.3.1.5 Others Organotin Reagents 222
6.3.2 Nucleophilic Addition onto Imines and Related Compounds 224
6.3.2.1 Reactions with Imines 224
6.3.2.2 Other Imino Substrates 225
6.3.2.3 Catalytic Enantioselective Addition 227
6.4 Radical Reactions of Organotins 227
6.4.1 Introduction 227
6.4.2 Allyltins 227
6.4.2.1 Mechanistic Overview 227
6.4.2.2 Functionalized Allyltins 229
6.4.3 Other Organotin Reagents 230
6.4.3.1 Tetraorganotins 230
6.4.3.2 Modified Organotins 231
6.4.4 The Stereoselective Approach 231
6.5 Transmetallations 232
6.5.1 Introduction 232
6.5.2 Tin-to-lithium Exchange 233
6.5.2.1 -Heterosubstituted Alkyltins 233
6.5.2.2 Alkenyltins 235
6.5.3 Tin to Other Metal Exchanges 236
6.6 Conclusion 236
7 Polyfunctional Zinc Organometallics for Organic Synthesis
Paul Knochel, Helena Leuser, Liu-Zhu Gong, Sylvie Perrone, and Florian F. Kneisel 		251
7.1 Introduction 251
7.2 Methods of Preparation of Polyfunctional Organozinc Reagents 252
7.2.1 Classification 252
7.2.2 Preparation of Polyfunctional Organozinc Halides 252
7.2.2.1 Preparation by the Oxidative Addition to Zinc Metal 252
7.2.2.2 Preparation of Organozinc Halides using Transmetallation Reactions 261
7.2.3 Preparation of Diorganozincs 270
7.2.3.1 Preparation via an I/Zn Exchange 270
7.2.3.2 The Boron–Zinc Exchange 273
7.2.3.3 Hydrozincation of Alkenes 278
7.2.4 Diverse Methods of Preparation of Allylic Zinc Reagents 278
7.2.5 Preparation of Lithium Triorganozincates 281
7.3 Reactions of Organozinc Reagents 282
7.3.1 Uncatalyzed Reactions 283
7.3.2 Copper(I)-catalyzed Reactions 292
7.3.2.1 Substitution Reactions 293
7.3.2.2 Acylation Reactions 303
7.3.2.3 Addition Reactions 305
7.3.2.4 Michael Additions 309
7.3.3 Palladium- and Nickel-catalyzed Reactions 316
7.3.4 Reactions Catalyzed by Titanium and Zirconium(IV) Complexes 326
7.3.5 Reactions of Zinc Organometallics Catalyzed by Cobalt, Iron or Manganese Complexes 332
7.4 Conclusion 333
Index I 1
Volume 2 347
8 Polyfunctional 1,1-Organodimetallic for Organic Synthesis
Seijiro Matsubara 		347
8.1 Introduction 347
8.2 gem-Dizincio Compounds 348
8.2.1 General View 348
8.2.2 Methylenation with bis(iodozincio)methane 351
8.2.3 gem-Dizincio Species from gem-Dihaloalkane 357
8.2.4 Alkenylsilane, -Germane, -and Borane Synthesis 360
8.2.5 Stepwise Coupling Reaction with Two Different Electrophiles 361
8.2.6 Reaction with Acyl Chloride and Cyanide 364
8.2.7 1,4-Addition of bis(iodozincio)methane to , -unsaturated ketones 365
8.2.8 Cyclopropanation Reaction 367
8.2.9 Pinacolone Rearrangement with Unusual Diastereospecificity 368
8.2.10 gem-Dizincio Reagent Working as Carbenoid 370
8.3 Chromium Compounds 371
8.3.1 General View 371
8.3.2 Alkylidenation 371
8.3.3 -Halogen Atom Substituted gem-Dichromium Reagent 373
8.4 Conclusion 375
9 Polyfunctional Organocopper Reagents for Organic Synthesis
Paul Knochel, Xiaoyin Yang, and Nina Gommermann 		379
9.1 Introduction 379
9.2 Preparation of Functionalized Organocopper Reagents 379
9.2.1 Preparation by the Direct Insertion of Activated Copper 379
9.2.2 Preparation by a Halogen–Copper Exchange Reaction 382
9.2.3 Preparation of Functionalized Copper Reagents Starting from Organolithium Reagents 386
9.2.4 Preparation of Functionalized Alkenylcopper Derivatives Starting from Organozirconium Compounds 389
9.3 Applications of Functionalized Copper Reagents 391
9.4 Conclusion 394
10 Functional Organonickel Reagents
Tien-Yau Luh and Li-Fu Huang 		397
10.1 Introduction 397
10.2 Homocoupling Reactions 397
10.3 Cross-coupling Reactions 400
10.3.1 Kumada–Corriu Reactions 401
10.3.2 Negishi Reaction 403
10.3.3 Suzuki Reaction 405
10.3.4 Stille Coupling 407
10.3.5 Heck Reaction 407
10.3.6 Miscellaneous Coupling Reactions 407
10.3.7 Aliphatic Substrates 409
10.4 Carbozincation Reactions 411
10.5 Cycloadditions 413
10.5.1 [2 + 2] Cycloaddition 413
10.5.2 [4 + 2] Cycloaddition 414
10.5.3 [4 + 4] Cycloaddition 415
10.5.4 [2 + 2 + 2] Cycloaddition 416
10.5.5 [3 + 2 + 2] Cycloaddition 418
10.5.6 [4 + 2 + 1] Cycloaddition 419
10.6 Intramolecular Coupling of Enynes or Alkynes 420
10.7 Reactions of Enones with Alkynes 422
10.8 Reaction of Simple Aldehydes or Ketones with Alkynes 429
10.9 Miscellaneous Reactions 436
10.10 Conclusion 443
11 Polyfunctional Metal Carbenes for Organic Synthesis
Karl Heinz Dötz, Alexander Koch, and Martin Werner 		451
11.1 Introduction 451
11.2 Chromium-Templated Cycloaddition Reactions 451
11.2.1 Cyclopropanation 452
11.2.2 Benzannulation 455
11.2.3 Cyclization of Chromium Oligoene(-yne) Carbenes 461
11.3 Reactions of Higher Nuclearity Chromium and Tungsten Carbenes 467
11.4 Metathesis Reactions Catalyzed by Group VI and VIII Metal Carbenes 473
11.5 Transmetallation 477
11.6 Metal Carbenes in Peptide Chemistry 481
11.7 Stereoselective Syntheses with Sugar Metal Carbenes 483
11.8 Sugar Metal Carbenes as Organometallic Gelators 495
11.9 Conclusion 496
12 Functionalized Organozirconium and Titanium in Organic Synthesis
Ilan Marek and Helena Chechik-Lankin 		503
12.1 Introduction 503
12.2 Functionalized Organozirconocene Derivatives 503
12.2.1 Preparation of Functionalized Alkenylzirconocene Derivatives 503
12.2.2 Preparation of Functionalized Alkylzirconocene Derivatives 511
12.2.3 Preparation and Reactivity of Acylzirconocene Derivatives 514
12.2.4 Preparation of Functionalized Low-valent Zirconocene Derivatives 519
12.3 Functionalized Organotitanium Derivatives 520
12.3.1 Preparation of Functionalized Substrates via Titanocene Derivatives 521
12.3.1.1 Intramolecular Reductive Cyclization 521
12.3.1.2 Allenylation of Functionalized Carbonylic Compounds 525
12.3.2 Preparation of Functionalized Substrates via Titanium (ii) Alkoxide Derivatives 526
12.3.2.1 Generation of -2-Alkene, -2-Alkyne Complexes and their Utilization as Vicinal Dianionic Species 526
13 Manganese Organometallics for the Chemoselective Synthesis of Polyfunctional Compounds
Gérard Cahiez and Florence Mahuteau-Betzer 		541
13.1 Introduction 541
13.2 Preparation of Organomanganese Compounds 541
13.2.1 Preparation of Organomanganese Compounds by Transmetallation 541
13.2.2 Preparation of Organomanganese Compounds from Mn0 543
13.3 1,2-Addition to Aldehydes and Ketones 544
13.3.1 Chemoselective 1,2-Addition of Organomanganese Reagents to Carbonyl Compounds 544
13.3.2 Manganese-Mediated Barbier- and Reformatsky-like Reactions 547
13.4 Preparation of Ketones by Acylation of Organomanganese Reagents 548
13.4.1 Acylation of Organomanganese Reagents 548
13.4.2 Manganese-Catalyzed Acylation of Grignard Reagents 554
13.5 1,4-Addition of Organomanganese Reagents to Enones 555
13.6 Transition-Metal-Catalyzed Cross-coupling Reactions 559
13.6.1 Copper-Catalyzed Cross-coupling Reactions 559
13.6.2 Iron-Catalyzed Cross-coupling Reactions 560
13.6.3 Palladium-Catalyzed Cross-coupling Reactions 561
13.6.4 Nickel-Catalyzed Cross-coupling Reactions 562
13.7 Mangan-Mediated Cross-coupling Reactions 563
13.7.1 Mangan-Catalyzed or -Mediated Cross-coupling Reactions 563
13.7.2 Mixed (Mn/Cu)-Catalyzed Cyclizations 565
14 Polyfunctional Electrophilic Multihapto-Organometallics forOrganicSynthesis
G. Richard Stephenson 		569
14.1 Introduction to Multihapto-Complexes and Discussion of Nomenclature 569
14.2 Classes of Nucleophile Addition Pathways to Multihapto-Complexes 571
14.3 Unsymmetrically Placed Substituents in Stoichiometric Electrophilic Multihapto-Complexes 575
14.3.1 Electrophilic 2 Complexes 575
14.3.2 Electrophilic 3 Complexes 576
14.3.3 Electrophilic 4 Complexes 577
14.3.4 Electrophilic 5 Complexes 578
14.3.5 Electrophilic 6 Complexes 585
14.3.6 Branched Electrophilic Systems 589
14.3.7 Conjugate Addition to Unsaturated Extensions of Electrophillic Multihapto-Complexes 590
14.3.8 Internal Addition of Nucleophiles 592
14.4 Caveats and Cautions 595
14.5 Examples of the Use of Electrophilic Multihapto-Complexes in Organic Synthesis 598
14.5.1 Alkyl-derived Directing Effects in Synthetic Applications of Multihapto-Complexes 598
14.5.2 Electron-withdrawing Groups with -Directing Effects in Synthetic Applications of Multihapto-Complexes 599
14.5.3 Aryl Substituents with -Directing Effects in Synthetic Applications of Multihapto-Complexes 600
14.5.4 Electron-donating Groups with Ipso-Directing Effects in Synthetic Applications of Multihapto-Complexes 611
14.5.5 Electron-donating Groups with -Directing Effects in Synthetic Applications of Multihapto-Complexes 612
14.5.6 Electron-donating Groups with -Directing Effects in Synthetic Applications of Multihapto-Complexes 614
14.5.7 Halogen Substituents with Ipso-Directing Effects in Synthetic Applications of Multihapto-Complexes 615
14.5.8 Remote Nucleophile Addition in Synthetic Applications of Multihapto-Complexes 615
14.5.9 Design Efficiency in the Synthetic Applications of Multihapto-Complexes 616
14.6 Conclusions 617
15 Polyfunctional Zinc, Cobalt and Iron Organometallics Prepared byElectrosynthesis
Jacques Périchon and Corinne Gosmini 		629
15.1 Introduction 629
15.2 Electrochemical Device and General Reaction Conditions 632
15.3 Electrochemical Synthesis Involving Functionalized Organo-Cobalt or-IronIntermediates Derivatives 633
15.3.1 Introduction 633
15.3.2 Carbon–Carbon Bond Formation Using Electrogenerated Functionalized Organocobalt Species 635
15.3.2.1 Electrosynthesis of Dissymmetric Biaryls 635
15.3.2.2 Electrochemical Addition of Aryl Halides onto Activated Olefins 637
15.3.2.3 Electrochemical Vinylation of Aryl Halides using Vinylic Acetates 638
15.3.2.4 Cross-coupling between Aryl or Heteroaryl Halides and Allylic Acetates orCarbonates 639
15.3.3 Carbon–Carbon Bond using Electrogenerated Functionalized Organometallic Iron 640
15.3.3.1 Coupling of Activated Aliphatic Halides with Carbonyl Compounds 640
15.3.3.2 Electrochemical Allylation of Carbonyl Compounds by Allylic Acetates 641
15.3.3.3 Conclusion 642
15.4 Electrosynthesis of Functionalized Aryl- or Heteroarylzinc Compounds and their Reactivity 642
15.4.1 Introduction 642
15.4.2 Electrosynthesis of Aryl or Heteroaryl Zinc Species from the Corresponding Halide via a Nickel Catalysis [14] 643
15.4.3 Electrosynthesis of Aryl or Heteroaryl Zinc Species from the Corresponding Halide via a Cobalt Catalysis 645
15.4.3.1 In DMF/Pyridine or CH3CN/Pyridine as Solvent [15] 645
15.4.3.2 In CH3CN as Solvent 648
15.4.3.3 Conclusion 650
15.5 General Conclusion 650
Index I 1

 
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