Metal-catalyzed cross-coupling reactions and more : Volume 1

Edited by

Armin de Meijere, Stefan Brase, and ¨

Martin Oestreich

Metal-Catalyzed Cross-Coupling Reactions

and More

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Edited by Armin de Meijere, Stefan Brase, and ¨

Martin Oestreich

Metal-Catalyzed Cross-Coupling Reactions

and More

Volume 1

The Editors

Armin de Meijere

Institut fur Organische und ¨

Biomolekulare Chemie

der Georg-August-Universitat ¨

Tammannstr. 2

37077 Gottingen ¨

Germany

Stefan Brase ¨

Institute of Organic Chemistry &

Institute of Toxicology and Genetics

Karlsruhe Institute of Technology

Fritz-Haber-Weg 6

76131 Karlsruhe

Germany

Martin Oestreich

Institut fur Chemie ¨

Technische Universitat Berlin ¨

Strasse des 17. Juni 115

10623 Berlin

Germany

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V

Contents to Volume 1

Preface XV

List of Contributors XVII

1 Mechanistic Aspects of Metal-Catalyzed C,C- and C,X-Bond Forming

Reactions 1

Antonio M. Echavarren and Anna Homs

1.1 Mechanisms of Cross-Coupling Reactions 1

1.1.1 The Earlier Mechanistic Proposal: The Stille Reaction 2

1.1.2 The Oxidative Addition 3

1.1.2.1 Cis-Complexes in the Oxidative Addition 4

1.1.2.2 The Role of Alkene and Anionic Ligands 5

1.1.2.3 Cross-Couplings in the Presence of Bulky Phosphines 6

1.1.2.4 N-Heterocyclic Carbenes as Ligands 12

1.1.2.5 Palladacycles as Catalysts 13

1.1.2.6 Involvement of Pd(IV) in Catalytic Cycles 14

1.1.2.7 Oxidative Addition of Stannanes to Pd(0) 16

1.1.3 The Transmetallation in the Stille Reaction 16

1.1.3.1 Isolation of the Transmetallation Step 16

1.1.3.2 Dissociative Mechanistic Proposals 18

1.1.3.3 Cyclic and Open Associative Transmetallation 19

1.1.3.4 The Copper Effect 23

1.1.3.5 Transmetallation in the Suzuki–Miyaura Reaction 24

1.1.3.6 Transmetallation in the Negishi Reaction 27

1.1.3.7 Transmetallation in the Hiyama Reaction 28

1.1.3.8 Couplings Catalyzed by Copper and Gold 30

1.1.3.9 Couplings Catalyzed by Iron and Cobalt 32

1.1.4 Reductive Elimination 33

1.2 Palladium-Catalyzed α-Arylation of Carbonyl Compounds and

Nitriles 35

1.3 Formation of C–X (X = N, O, S) Bonds in Metal-Catalyzed

Reactions 36

VI Contents

1.3.1 Reductive Elimination to Generate C–N, C–O, and C–S Bonds from

Organopalladium(II) Complexes 39

1.3.2 Nickel- and Copper-Catalyzed Formation of C–X Bonds 44

1.4 Summary and Outlook 46

List of Abbreviations 46

References 47

2 State-of-the-Art in Metal-Catalyzed Cross-Coupling Reactions of

Organoboron Compounds with Organic Electrophiles 65

Jack C.H. Lee and Dennis G. Hall

2.1 Introduction 66

2.1.1 Catalytic Cycle 66

2.1.2 Improvements toward More Efficient Cross-Coupling Conditions 69

2.1.2.1 Development of New Phosphine and NHC Ligands 69

2.1.2.2 Usage of Masked Boron Derivatives as Cross-Coupling Partners 70

2.1.2.3 Lewis Acids as Additives 72

2.1.2.4 Adjusting the Nucleophilicity of Organoboron Cross-Coupling

Partners 73

2.1.2.5 Copper Salts as Additives 74

2.2 Advances in Cross-Coupling Reactions for the Formation of

C(sp2)–C(sp2) Bonds 75

2.2.1 Background 75

2.2.2 Recent Developments in the Use of New Electrophilic Coupling

Partners 75

2.2.2.1 Chlorides 75

2.2.2.2 Fluorides 79

2.2.2.3 Pseudohalides 82

2.2.3 Recent Developments in Organoboron Cross-Coupling Partners 92

2.2.3.1 Trifluoroborate Salts 93

2.2.3.2 N-Methyliminodiacetic Acid (MIDA) Boronates 97

2.2.3.3 Other Organoboron Cross-Coupling Partners 99

2.2.4 Synthesis of Enantiomerically Enriched Atropisomers 101

2.3 Advances in the Cross-Coupling Reactions for the Formation of

C(sp3)–C(sp2) or C(sp3)–C(sp3) Bonds 103

2.3.1 Background 103

2.3.1.1 Stereochemistry 104

2.3.2 Cross-Couplings between Unsaturated sp2 Carbon Centers and sp3

Carbon Centers 105

2.3.2.1 Cross-Couplings between sp3 Alkyl Halides and sp2 Alkenyl or Aryl

Boron Derivatives 105

2.3.2.2 Cross-Couplings between sp3 Alkyl Boron Derivatives with sp2 Alkenyl

or Aryl Halides 110

2.3.3 Cross-Couplings between sp3 Carbon Centers with sp3 Carbon

Centers 117

2.3.3.1 Cross-Couplings between Achiral Substrates 117

Contents VII

2.3.3.2 Stereoselective Cross-Coupling Reactions of sp3 Alkyl Halides with sp3

Alkylboranes 118

2.4 Experimental Procedures 121

2.4.1 2,6-Dimethoxy-2

,6

-dimethylbiphenyl (55) 121

2.4.2 4-Methoxybiphenyl (R = C(O)NEt2, R = H, Ar =

4-methoxyphenyl) 121

2.4.3 1-Phenylnaphthalene (ROH = naphthol, Ar = Ph) 122

2.4.4 1-(3,5-Dimethoxyphenyl)-5-phenylpentan-3-one (Ralkyl-BF3K = 197,

R1 = CH2CH2Ph, R = 3,5-dimethoxybenzene) 122

2.4.5 1-Phenyl-1-(4-acetylphenyl-ethane (ArI = 4-iodoacetophenone) 122

2.4.6 Naphthalene-1,8-diamido (dan) derivative (Ar = Ph) 123

2.4.7 2-Methyl-5-phenylpentyl benzyl(phenyl)carbamate (Ralkyl = Me,

X = Br, R

alkyl = CH2CH2CH2Ph) 123

2.5 Summary and Outlook 124

References 124

3 Pd-Catalyzed Cross-Coupling with Organometals Containing Zn, Al, Zr,

and so on – The Negishi Coupling and Its Recent Advances 133

Shiqing Xu, Hirofumi Kamada, Eun Hoo Kim, Akimichi Oda, and

Ei-ichi Negishi

3.1 Background and Discovery 134

3.1.1 Why Metals? Why Transition Metals? 134

3.1.2 Why Transition Metal-Catalyzed Organometallic Reactions? 136

3.2 Discovery of the Pd- or Ni-Catalyzed Cross-Coupling Reactions of

Organometals Containing Zn, Al, Zr, and B 137

3.3 The Current Scope of the Pd- or Ni-Catalyzed Cross-coupling and Its

Application to the Synthesis of Natural Products and Other Complex

Organic Compounds 154

3.3.1 Cross-Coupling between Two Unsaturated (Aryl, Alkenyl, and/or

Alkynyl) Groups 156

3.3.1.1 Aryl–Aryl Coupling 156

3.3.1.2 Aryl–Alkenyl and Alkenyl–Aryl Couplings 158

3.3.1.3 Alkenyl–Alkenyl Coupling 159

3.3.1.4 Pd-Catalyzed Alkynylation 191

3.3.2 Cross-Coupling Involving One Allyl, Benzyl, or Propargyl Group 197

3.3.2.1 1,4-Dienes via Pd-Catalyzed Alkenyl–Allyl and Allyl–Alkenyl Coupling

and 1,4-Enynes by Pd-Catalyzed Alkynyl–Allyl Coupling 197

3.3.2.2 Benzyl–Aryl, Aryl–Benzyl Coupling 203

3.3.2.3 Allylbenzene Derivatives via Pd-Catalyzed Alkenyl–Benzyl Coupling

and Aryl–Allyl and Allyl–Aryl Coupling 204

3.3.2.4 Benzylated Alkynes via Pd-Catalyzed Alkynyl–Benzyl Coupling and

Aryl–Propargyl as well as Propargyl–Aryl Coupling 204

3.3.2.5 1,4-Diynes via Alkynyl–Propargyl Coupling 207

VIII Contents

3.3.2.6 Synthesis of Natural Products Containing 1,4-Diene and Allylated

Arenes by Pd-Catalyzed Allylation, Benzylation, and

Propargylation 208

3.3.3 Cross-Coupling between Two Allyl, Benzyl, and/or Propargyl

Groups 210

3.3.3.1 1,5-Dienes and 1,5-Enynes via Pd-Catalyzed Cross-Couplings with

Allyl, Benzyl, Propargyl Electrophiles 210

3.3.3.2 1,5-Dienes and 1,5-Enynes via Pd-Catalyzed Homoallyl–Alkenyl

Coupling and Homopropargyl–Alkenyl Coupling 212

3.3.3.3 Bibenzyls, Homoallylarenes, 1,5-Dienes, Homopropargylarenes, and

1,5-Enynes via Pd-Catalyzed Negishi Coupling 214

3.3.4 Cross-Coupling Involving Alkylmetals and/or Alkyl Electrophiles

Other Than Those Containing Allyl, Benzyl, and/or Propargyl

Groups 216

3.3.4.1 Pd-Catalyzed Alkyl–Alkyl Coupling 219

3.3.4.2 Ni-Catalyzed Alkyl–Alkyl Coupling 221

3.3.4.3 Catalytic Asymmetric Cross-Coupling Reactions with Secondary Alkyl

Halides 223

3.3.5 Pd-Catalyzed Acylation, Cyanation, and α-Substitution of Enolates and

Related Derivatives 227

3.3.5.1 Pd-Catalyzed Acylation 227

3.3.5.2 Pd-Catalyzed Cyanation 232

3.3.5.3 Pd-Catalyzed α-Substitution of Enolates and Related Derivatives 233

3.4 Zr-Catalyzed Asymmetric Carboalumination of Alkenes (ZACA)

ZACA–Pd- or Cu-Catalyzed Cross-Coupling Sequential Processes as a

General Route to Enantiomerically Enriched Chiral Organic

Compounds 243

3.4.1 Zirconium-Catalyzed Asymmetric Carboalumination of Alkenes

(ZACA Reaction) 243

3.4.1.1 Historical and Mechanistic Background of Carbometallation of

Alkenes and Alkynes with Alkylzirconocene Derivatives 244

3.4.1.2 Catalytic Asymmetric Carbometallation of Alkenes Proceeding via

Dzhemilev Ethylmagnesiations 246

3.4.2 Current Summary of Development and Application of the ZACA

Reaction and Conclusion 249

3.4.2.1 ZACA–Pd-Catalyzed Cross-Coupling Sequential Processes for the

Synthesis of Deoxypolypropionates and Related Compounds 249

3.4.2.2 ZACA–Lipase-Catalyzed Acetylation–Pd- or Cu-Catalyzed

Cross-Coupling Synergy to Chiral Organic Compounds 253

3.5 Representative Experimental Procedures 260

3.5.1 (2Z,4S)-5-(tert-Butyldimethylsilyloxy)-2-phenyl-4-methyl-2-

pentene 260

3.5.2 (2Z,4E,6E)-Ethyl Trideca-2,4,6-trienoate 260

3.5.3 (2Z)-2-Allyl-3,7-dimethylocta-2,6-dien-1-ol 260

3.5.4 Ethyl 2-(4-Phenylbuta-1,3-diynyl)benzoate 261

Contents IX

3.5.4.1 (E)-1-Chloro-4-phenyl-1-buten-3-yne 261

3.5.4.2 Ethyl 2-(4-Phenylbuta-1,3-diynyl)benzoate 261

3.5.5 O-tert-Butyldiphenylsilyl-protected

(3S,5E)-3,9-Dimethyl-6-isopropyl-5,8-decadien-1-ol 261

3.5.5.1 (1E)-1-Iodo-2-isopropyl-5-methyl-1,4-hexadiene 261

3.5.5.2 O-tert-Butyldiphenylsilyl-protected

(3S,5E)-3,9-Dimethyl-6-isopropyl-5,8-decadien-1-ol 262

3.5.6 1,3-Diphenylpropyne 262

3.5.7 (4S)-4-Phenyl-1-pentene 263

3.5.8 (R)-2-Phenylpropan-1-ol 263

Acknowledgments 263

References 264

4 Carbon–Carbon Bond Forming Reactions Mediated by Organozinc

Reagents 279

Fabrice Chemla, Franck Ferreira, Olivier Jackowski, Laurent Micouin, and

Alejandro Perez-Luna

4.1 Introduction 279

4.2 Methods of Preparation of Zinc Organometallics 280

4.2.1 Direct Insertion of Zn(0) into Organohalides 280

4.2.2 Transmetallation Reactions 282

4.2.2.1 Transmetallation Reactions with Main-Group and Transition Metal

Organometallics 282

4.2.2.2 Boron–Zinc Exchange Reactions 285

4.2.3 Direct Zincation Reactions 287

4.2.4 Halogen–Zinc Exchange Reactions 288

4.2.5 Hydro- and Carbozincation Reactions 290

4.3 Uncatalyzed Cross-Coupling Reactions of Organozinc Reagents 291

4.4 Copper-Catalyzed Cross-Coupling Reactions of Organozinc

Reagents 293

4.4.1 Cross-Coupling with C(sp)- or C(sp2)-Electrophiles 293

4.4.2 Cross-Coupling Reactions with C(sp3)-Electrophiles 295

4.5 Transition-Metal-Catalyzed Cross-Coupling Reactions of Organozinc

Reagents 296

4.5.1 Cross-Coupling Reactions of C(sp2)-Organozinc Reagents 297

4.5.1.1 Palladium-Catalyzed Cross-Coupling Reactions 297

4.5.1.2 Nickel-Catalyzed Cross-Coupling Reactions 311

4.5.1.3 Rhodium-Catalyzed Cross-Coupling Reactions 315

4.5.1.4 Cobalt-Catalyzed Cross-Coupling Reactions 316

4.5.1.5 Iron-Catalyzed Cross-Coupling Reactions 317

4.5.2 Cross-Coupling Reactions of Alkynylzinc Reagents 318

4.5.2.1 Cross-Coupling with C(sp2)-Electrophiles 318

4.5.2.2 Cross-Coupling with C(sp3)-Electrophiles 320

4.5.3 Cross-Coupling Reactions of C(sp3)-Organozinc Reagents 321

4.5.3.1 Palladium-Catalyzed Cross-Coupling Reactions 322

X Contents

4.5.3.2 Nickel-Catalyzed Cross-Coupling Reactions 332

4.5.3.3 Platinum-Catalyzed Cross-Coupling Reactions 342

4.5.3.4 Iron-Catalyzed Cross-Coupling Reactions 343

4.5.3.5 Cobalt-Catalyzed Cross-Coupling Reactions 343

4.5.3.6 Rhodium-Catalyzed Cross-Coupling Reactions 344

4.6 Conclusions 345

4.7 Experimental Procedures 345

4.7.1 3-Ethoxycarbonylphenylzinc Iodide (7) 345

4.7.2 6-Carboethoxy-3,5-dimethylpyrimidinyl-5-zinc Chloride (27) 346

4.7.3 1-Hexenylmethylzinc (37) 346

4.7.4 Di(5-carboethoxy-5-hexenyl)zinc (39) 346

4.7.5 Di-(5-bromo-2,4-di(carboethoxy)phenyl)zinc (60) 347

4.7.6 Cyclohexylisopropylzinc (80) 347

4.7.7 10-Nitro-9-phenyldecyl Acetate (126) 347

4.7.8 2-Cyano-2

,4

,6

-triisopropylbiphenyl (140) 348

4.7.9 (2R,3S)-2-(3,4-Dimethoxyphenyl)-8-mesityl-5,7-dimethoxychroman￾3-ol (155) 348

4.7.10 2-(2-(Thiophen-2-yl)ethynyl)pyridine (173) 349

4.7.11 6,6-Diethoxy-2-phenyl-1-hexene (231) 349

4.7.12 Ethyl 4

-Methoxy-biphenyl-3-carboxylate (244) 349

4.7.13 Ethyl 4-(Furan-2-yl)benzoate (261) 350

4.7.14 Trimethyl((R)-3-p-tolylhept-1-ynyl)silane (268) 350

4.7.15 4-[2-(4-Methoxyphenyl)pyrimidin-4-yl]benzonitrile (286) 350

4.7.16 3-Cycloheptyl-2-methylprop-2-ene (292) 351

4.7.17 Ethyl 4-(Phenylethynyl)benzoate (301) 351

4.7.18 tert-Butyl((cis-3-(4-((tert-butyldimethylsilyl)oxy)but-1-yn-1-yl)

cyclohexyl)oxy)dimethylsilane (333) 351

4.7.19 cis-tert-Butyl 2-(4-Cyanophenyl)-4-phenylpiperidine-1-carboxylate

(352) 352

4.7.20 1-(((E)-Dodec-4-enyloxy)methyl)benzene (364) 352

4.7.21 Ethyl 6-Phenylhex-5-ynoate (379) 352

4.7.22 8-Oxo-8-phenyloctyl Pivalate (403) 353

4.7.23 7-Phenylheptanoic Acid Diethylamide (441) 353

4.7.24 Ethyl 4-Isopropylbenzoate (456) 353

Acknowledgments 354

List of Abbreviations 354

References 355

5 Carbon–Carbon-Bond-Forming Reactions Mediated by

Organomagnesium Reagents 365

Fabrice Chemla, Franck Ferreira, Alejandro Perez-Luna, Laurent Micouin,

and Olivier Jackowski

5.1 Introduction 365

5.2 Methods of Preparation of Magnesium Organometallics 366

5.2.1 Direct Insertion of Magnesium 366

Contents XI

5.2.2 Halogen–Magnesium Exchange Reactions 366

5.2.3 Direct Magnesiation Reactions 368

5.3 Transition-Metal-Catalyzed Cross-Coupling Reactions of

Organomagnesium Reagents 370

5.3.1 Cross-Coupling of C(sp2)-Organomagnesium Reagents 372

5.3.1.1 Nickel-Catalyzed Cross-Coupling Reactions 372

5.3.1.2 Palladium-Catalyzed Cross-Coupling Reactions 375

5.3.1.3 Iron-Catalyzed Cross-Coupling Reactions 379

5.3.1.4 Cobalt-Catalyzed Cross-Coupling Reactions 383

5.3.1.5 Manganese-Catalyzed Cross-Coupling Reactions 383

5.3.1.6 Rhodium-Catalyzed Cross-Coupling Reactions 383

5.3.2 Cross-Coupling Reactions of C(sp)-Organomagnesium

Reagents 384

5.3.2.1 Palladium-Catalyzed Cross-Coupling Reactions 385

5.3.2.2 Cobalt-Catalyzed Cross-Coupling Reactions 386

5.3.2.3 Manganese-Catalyzed Oxidative Cross-Coupling Reactions 388

5.3.2.4 Nickel-Catalyzed Cross-Coupling Reactions 389

5.3.3 Cross-Coupling Reactions of C(sp3)-Organomagnesium

Reagents 390

5.3.3.1 Nickel-Catalyzed Cross-Coupling Reactions 391

5.3.3.2 Iron-Catalyzed Cross-Coupling Reactions 398

5.3.3.3 Palladium-Catalyzed Cross-Coupling Reactions 404

5.3.3.4 Copper-Catalyzed Cross-Coupling Reactions 406

5.3.3.5 Cobalt-Catalyzed Reactions 408

5.3.3.6 Manganese-Catalyzed Cross-Coupling Reactions 410

5.3.3.7 Silver-Catalyzed Cross-Coupling Reactions 410

5.4 Conclusions 411

5.5 Experimental Procedures 411

5.5.1 Ethyl 3

-Bromo-4

-[(tert-butoxycarbonyl)oxy]biphenyl-4-

carboxylate (3) 411

5.5.2 (2-Bromocyclopent-1-en-1-yl)(cyclohexyl)methanol (13) 412

5.5.3 Diethyl 4-Bromo-6-iodoisophthalate (29) 412

5.5.4 4-Methoxybiphenyl (41) 413

5.5.5 2-Phenyl-(2

-phenyl)-4-methylquinoline (69) 413

5.5.6 9-Methylenepentadec-7-yne (144) 414

5.5.7 Trimethyl(3-p-tolylprop-1-ynyl)silane (152) 414

5.5.8 1-(1-Heptynyl)-4-methoxybenzene (155) 414

5.5.9 N,N-5-Trimethylnaphthalen-1-amine (174) 415

5.5.10 N,N-Diethyldecanamide (200) 415

5.5.11 (E)-12-Acetoxydodec-5-ene (210) 415

5.5.12 2-tert-Butyl-4-tert-pentyl-6-phenyl-1,3,5-triazine (254) 416

Acknowledgments 416

List of Abbreviations 416

References 417

XII Contents

6 Organotin Reagents in Cross-Coupling Reactions 423

Bel´en Mart´ın-Matute, K´alm´an J. Szab´o, and Terence N. Mitchell

6.1 Introduction 423

6.2 Mechanism and Methodology 424

6.2.1 Mechanism 424

6.2.2 Methodology 428

6.2.2.1 Reaction Medium 429

6.2.2.2 New Ligands, Catalysts, and Additives 429

6.2.2.3 New Organic and Organotin Coupling Partners 434

6.2.2.4 Polymer-Supported Stille Chemistry 435

6.2.2.5 Other Advances in Methodology 436

6.3 Natural Product Synthesis 443

6.3.1 Intramolecular Couplings 444

6.3.2 Intermolecular Couplings 446

6.3.2.1 Vinyl–Vinyl Couplings 446

6.3.2.2 Other Couplings Involving Vinyltins 448

6.3.2.3 Couplings of Heterocyclic Organotins 449

6.3.2.4 Other Intermolecular Couplings 449

6.4 Organic Synthesis 450

6.4.1 Vinyl–Vinyl Couplings 450

6.4.2 Other Couplings Involving Vinyltins 451

6.4.3 Couplings of Aryltins 454

6.4.4 Couplings of Heterocyclic Organotins 455

6.4.5 Couplings of Alkynyltins 456

6.4.6 Couplings of Miscellaneous Organotins 457

6.5 Polymer Chemistry 457

6.5.1 Materials Based on Polythiophene (or Polyselenophene)

Backbones 458

6.5.2 Materials Based on Thiophene in Combination with Other Repeating

Units 459

6.5.3 Materials Based on Pyrrole and Furan 460

6.5.4 Polyphenylenevinylene and Related Materials 460

6.5.5 Other Materials 461

6.6 Inorganic Synthesis 461

6.6.1 Couplings of Vinyltins 461

6.6.2 Couplings of Aryltins 462

6.6.3 Couplings of Heterocyclic Organotins 462

6.6.4 Couplings of Alkynyltins 462

6.7 Conclusions 463

6.8 Experimental Procedures 464

6.8.1 Spirocyclization by Grigg et al. 464

6.8.2 4,4-Dicyano-2,7-dimethyl-5-phenylocta-1,7-diene (R=Me) 464

6.8.3 4,4

-Bis[5-ethynyl(5

-methyl-2,2

-bipyridyl)]-1,1

-biphenyl 464

6.8.4 Pentacarbonyl[1-dimethylamino-7-trimethylsilyl-2,4,6-

heptatriynylidene]tungsten 465

Contents XIII

List of Abbreviations 465

References 465

Contents to Volume 2

List of Contributors XIII

7 Organosilicon Compounds in Cross-Coupling Reactions 475

Scott E. Denmark and Ramzi F. Sweis

8 Cross-Coupling of Organyl Halides with Alkenes – The Heck

Reaction 533

Stefan Br¨ase and Armin de Meijere

9 Cross-Coupling Reactions to sp Carbon Atoms 665

Tobias A. Schaub and Milan Kivala

10 Carbometallation Reactions 763

Ilan Marek and Yury Minko

11 Palladium-Catalyzed 1,4-Additions to Conjugated Dienes 875

Jan-Erling B¨ackvall

12 Cross-Coupling Reactions via π-Allylmetal Intermediates 925

Anton Bayer and Uli Kazmaier

Contents to Volume 3

List of Contributors XIII

13 Palladium-Catalyzed Aromatic Carbon–Nitrogen Bond Formation 995

Jan Paradies

14 The Directed Ortho Metallation (DoM)–Cross-Coupling Nexus.

Synthetic Methodology for the Formation of Aryl–Aryl and

Aryl–Heteroatom–Aryl Bonds 1067

Victor Snieckus and Eric J.-G. Anctil

15 Transition-Metal-Catalyzed Hydroamination Reactions 1135

Laurel L. Schafer, Jacky C.-H. Yim, and Neal Yonson

16 Oxidative Functionalization of Alkenes 1259

Kilian Mu˜niz and Claudio Mart´ınez