Note: Intro -- Metal-Catalyzed Cross-Coupling Reactions and More -- Contents to Volume 1 -- Preface -- List of Contributors -- Chapter 1 Mechanistic Aspects of Metal-Catalyzed C,C- and C,X-Bond Forming Reactions -- 1.1 Mechanisms of Cross-Coupling Reactions -- 1.1.1 The Earlier Mechanistic Proposal: The Stille Reaction -- 1.1.2 The Oxidative Addition -- 1.1.2.1 Cis-Complexes in the Oxidative Addition -- 1.1.2.2 The Role of Alkene and Anionic Ligands -- 1.1.2.3 Cross-Couplings in the Presence of Bulky Phosphines -- 1.1.2.4 N-Heterocyclic Carbenes as Ligands -- 1.1.2.5 Palladacycles as Catalysts -- 1.1.2.6 Involvement of Pd(IV) in Catalytic Cycles -- 1.1.2.7 Oxidative Addition of Stannanes to Pd(0) -- 1.1.3 The Transmetallation in the Stille Reaction -- 1.1.3.1 Isolation of the Transmetallation Step -- 1.1.3.2 Dissociative Mechanistic Proposals -- 1.1.3.3 Cyclic and Open Associative Transmetallation -- 1.1.3.4 The Copper Effect -- 1.1.3.5 Transmetallation in the Suzuki-Miyaura Reaction -- 1.1.3.6 Transmetallation in the Negishi Reaction -- 1.1.3.7 Transmetallation in the Hiyama Reaction -- 1.1.3.8 Couplings Catalyzed by Copper and Gold -- 1.1.3.9 Couplings Catalyzed by Iron and Cobalt -- 1.1.4 Reductive Elimination -- 1.2 Palladium-Catalyzed α-Arylation of Carbonyl Compounds and Nitriles -- 1.3 Formation of C-X (X = N, O, S) Bonds in Metal-Catalyzed Reactions -- 1.3.1 Reductive Elimination to Generate C-N, C-O, and C-S Bonds from Organopalladium(II) Complexes -- 1.3.2 Nickel- and Copper-Catalyzed Formation of C-X Bonds -- 1.4 Summary and Outlook -- List of Abbreviations -- References -- Chapter 2 State-of-the-Art in Metal-Catalyzed Cross-Coupling Reactions of Organoboron Compounds with Organic Electrophiles -- 2.1 Introduction -- 2.1.1 Catalytic Cycle -- 2.1.2 Improvements toward More Efficient Cross-Coupling Conditions. , 2.1.2.1 Development of New Phosphine and NHC Ligands -- 2.1.2.2 Usage of Masked Boron Derivatives as Cross-Coupling Partners -- 2.1.2.3 Lewis Acids as Additives -- 2.1.2.4 Adjusting the Nucleophilicity of Organoboron Cross-Coupling Partners -- 2.1.2.5 Copper Salts as Additives -- 2.2 Advances in Cross-Coupling Reactions for the Formation of C(sp2)-C(sp2) Bonds -- 2.2.1 Background -- 2.2.2 Recent Developments in the Use of New Electrophilic Coupling Partners -- 2.2.2.1 Chlorides -- 2.2.2.2 Fluorides -- 2.2.2.3 Pseudohalides -- 2.2.3 Recent Developments in Organoboron Cross-Coupling Partners -- 2.2.3.1 Trifluoroborate Salts -- 2.2.3.2 N-Methyliminodiacetic Acid (MIDA) Boronates -- 2.2.3.3 Other Organoboron Cross-Coupling Partners -- 2.2.4 Synthesis of Enantiomerically Enriched Atropisomers -- 2.3 Advances in the Cross-Coupling Reactions for the Formation of C(sp3)-C(sp2) or C(sp3)-C(sp3) Bonds -- 2.3.1 Background -- 2.3.1.1 Stereochemistry -- 2.3.2 Cross-Couplings between Unsaturated sp2 Carbon Centers and sp3 Carbon Centers -- 2.3.2.1 Cross-Couplings between sp3 Alkyl Halides and sp2 Alkenyl or Aryl Boron Derivatives -- 2.3.2.2 Cross-Couplings between sp3 Alkyl Boron Derivatives with sp2 Alkenyl or Aryl Halides -- 2.3.3 Cross-Couplings between sp3 Carbon Centers with sp3 Carbon Centers -- 2.3.3.1 Cross-Couplings between Achiral Substrates -- 2.3.3.2 Stereoselective Cross-Coupling Reactions of sp3 Alkyl Halides with sp3 Alkylboranes -- 2.4 Experimental Procedures -- 2.4.1 2,6-Dimethoxy-2',6'-dimethylbiphenyl (55) -- 2.4.2 4-Methoxybiphenyl (R = C(O)NEt2, R' = H, Ar = 4-methoxyphenyl) -- 2.4.3 1-Phenylnaphthalene (ROH = naphthol, Ar = Ph) -- 2.4.4 1-(3,5-Dimethoxyphenyl)-5-phenylpentan-3-one (Ralkyl-BF3K = 197, R1 = CH2CH2Ph, R' = 3,5-dimethoxybenzene) -- 2.4.5 1-Phenyl-1-(4-acetylphenyl-ethane (ArI = 4-iodoacetophenone). , 2.4.6 Naphthalene-1,8-diamido (dan) derivative (Ar = Ph) -- 2.4.7 2-Methyl-5-phenylpentyl benzyl(phenyl)carbamate (Ralkyl = Me,X = Br, R'alkyl = CH2CH2CH2Ph) -- 2.5 Summary and Outlook -- References -- Chapter 3 Pd-Catalyzed Cross-Coupling with Organometals Containing Zn, Al, Zr, and so on - The Negishi Coupling and Its Recent Advances -- 3.1 Background and Discovery -- 3.1.1 Why Metals? Why Transition Metals? -- 3.1.2 Why Transition Metal-Catalyzed Organometallic Reactions? -- 3.2 Discovery of the Pd- or Ni-Catalyzed Cross-Coupling Reactions of Organometals Containing Zn, Al, Zr, and B -- 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 -- 3.3.1 Cross-Coupling between Two Unsaturated (Aryl, Alkenyl, and/or Alkynyl) Groups -- 3.3.1.1 Aryl-Aryl Coupling -- 3.3.1.2 Aryl-Alkenyl and Alkenyl-Aryl Couplings -- 3.3.1.3 Alkenyl-Alkenyl Coupling -- 3.3.1.4 Pd-Catalyzed Alkynylation -- 3.3.2 Cross-Coupling Involving One Allyl, Benzyl, or Propargyl Group -- 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 -- 3.3.2.2 Benzyl-Aryl, Aryl-Benzyl Coupling -- 3.3.2.3 Allylbenzene Derivatives via Pd-Catalyzed Alkenyl-Benzyl Coupling and Aryl-Allyl and Allyl-Aryl Coupling -- 3.3.2.4 Benzylated Alkynes via Pd-Catalyzed Alkynyl-Benzyl Coupling and Aryl-Propargyl as well as Propargyl-Aryl Coupling -- 3.3.2.5 1,4-Diynes via Alkynyl-Propargyl Coupling -- 3.3.2.6 Synthesis of Natural Products Containing 1,4-Diene and Allylated Arenes by Pd-Catalyzed Allylation, Benzylation, and Propargylation -- 3.3.3 Cross-Coupling between Two Allyl, Benzyl, and/or Propargyl Groups -- 3.3.3.1 1,5-Dienes and 1,5-Enynes via Pd-Catalyzed Cross-Couplings with Allyl, Benzyl, Propargyl Electrophiles. , 3.3.3.2 1,5-Dienes and 1,5-Enynes via Pd-Catalyzed Homoallyl-Alkenyl Coupling and Homopropargyl-Alkenyl Coupling -- 3.3.3.3 Bibenzyls, Homoallylarenes, 1,5-Dienes, Homopropargylarenes, and 1,5-Enynes via Pd-Catalyzed Negishi Coupling -- 3.3.4 Cross-Coupling Involving Alkylmetals and/or Alkyl Electrophiles Other Than Those Containing Allyl, Benzyl, and/or Propargyl Groups -- 3.3.4.1 Pd-Catalyzed Alkyl-Alkyl Coupling -- 3.3.4.2 Ni-Catalyzed Alkyl-Alkyl Coupling -- 3.3.4.3 Catalytic Asymmetric Cross-Coupling Reactions with Secondary Alkyl Halides -- 3.3.5 Pd-Catalyzed Acylation, Cyanation, and α-Substitution of Enolates and Related Derivatives -- 3.3.5.1 Pd-Catalyzed Acylation -- 3.3.5.2 Pd-Catalyzed Cyanation -- 3.3.5.3 Pd-Catalyzed α-Substitution of Enolates and Related Derivatives -- 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 -- 3.4.1 Zirconium-Catalyzed Asymmetric Carboalumination of Alkenes (ZACA Reaction) -- 3.4.1.1 Historical and Mechanistic Background of Carbometallation of Alkenes and Alkynes with Alkylzirconocene Derivatives -- 3.4.1.2 Catalytic Asymmetric Carbometallation of Alkenes Proceeding via Dzhemilev Ethylmagnesiations -- 3.4.2 Current Summary of Development and Application of the ZACA Reaction and Conclusion -- 3.4.2.1 ZACA-Pd-Catalyzed Cross-Coupling Sequential Processes for the Synthesis of Deoxypolypropionates and Related Compounds -- 3.4.2.2 ZACA-Lipase-Catalyzed Acetylation-Pd- or Cu-Catalyzed Cross-Coupling Synergy to Chiral Organic Compounds -- 3.5 Representative Experimental Procedures -- 3.5.1 (2Z,4S)-5-(tert-Butyldimethylsilyloxy)-2-phenyl-4-methyl-2-pentene -- 3.5.2 (2Z,4E,6E)-Ethyl Trideca-2,4,6-trienoate -- 3.5.3 (2Z)-2-Allyl-3,7-dimethylocta-2,6-dien-1-ol. , 3.5.4 Ethyl 2-(4-Phenylbuta-1,3-diynyl)benzoate -- 3.5.4.1 (E)-1-Chloro-4-phenyl-1-buten-3-yne -- 3.5.4.2 Ethyl 2-(4-Phenylbuta-1,3-diynyl)benzoate -- 3.5.5 O-tert-Butyldiphenylsilyl-protected (3S,5E)-3,9-Dimethyl-6-isopropyl-5,8-decadien-1-ol -- 3.5.5.1 (1E)-1-Iodo-2-isopropyl-5-methyl-1,4-hexadiene -- 3.5.5.2 O-tert-Butyldiphenylsilyl-protected (3S,5E)-3,9-Dimethyl-6-isopropyl-5,8-decadien-1-ol -- 3.5.6 1,3-Diphenylpropyne -- 3.5.7 (4S)-4-Phenyl-1-pentene -- 3.5.8 (R)-2-Phenylpropan-1-ol -- Acknowledgments -- References -- Chapter 4 Carbon-Carbon Bond Forming Reactions Mediated by Organozinc Reagents -- 4.1 Introduction -- 4.2 Methods of Preparation of Zinc Organometallics -- 4.2.1 Direct Insertion of Zn(0) into Organohalides -- 4.2.2 Transmetallation Reactions -- 4.2.2.1 Transmetallation Reactions with Main-Group and Transition Metal Organometallics -- 4.2.2.2 Boron-Zinc Exchange Reactions -- 4.2.3 Direct Zincation Reactions -- 4.2.4 Halogen-Zinc Exchange Reactions -- 4.2.5 Hydro- and Carbozincation Reactions -- 4.3 Uncatalyzed Cross-Coupling Reactions of Organozinc Reagents -- 4.4 Copper-Catalyzed Cross-Coupling Reactions of Organozinc Reagents -- 4.4.1 Cross-Coupling with C(sp)- or C(sp2)-Electrophiles -- 4.4.2 Cross-Coupling Reactions with C(sp3)-Electrophiles -- 4.5 Transition-Metal-Catalyzed Cross-Coupling Reactions of Organozinc Reagents -- 4.5.1 Cross-Coupling Reactions of C(sp2)-Organozinc Reagents -- 4.5.1.1 Palladium-Catalyzed Cross-Coupling Reactions -- 4.5.1.2 Nickel-Catalyzed Cross-Coupling Reactions -- 4.5.1.3 Rhodium-Catalyzed Cross-Coupling Reactions -- 4.5.1.4 Cobalt-Catalyzed Cross-Coupling Reactions -- 4.5.1.5 Iron-Catalyzed Cross-Coupling Reactions -- 4.5.2 Cross-Coupling Reactions of Alkynylzinc Reagents -- 4.5.2.1 Cross-Coupling with C(sp2)-Electrophiles -- 4.5.2.2 Cross-Coupling with C(sp3)-Electrophiles. , 4.5.3 Cross-Coupling Reactions of C(sp3)-Organozinc Reagents.