Organozinc Derivatives and Transition Metal Catalysts : Formation of C-C Bonds by Cross-coupling

Organozinc reagents are less reactive than Grignard reagents but they are much more chemoselective. Since the Negishi cross-coupling reaction developed by Ei-ichi Negishi, who was awarded the Nobel Price in chemistry in 2010, a number of cross-coupling reactions involving organozinc derivatives and transition metal catalysts (Pd, Ni, Fe, Co, Cu, ...) has been tuned up to form C-C bonds. This book on "Organozinc derivatives and transition metal catalysts" has been written by experts in the field and is a complement to the book entitled "Grignard reagents and transition metal catalysts" (a De Gruyter book, edited by J. Cossy). Grignard reagents or organozinc reagents, that is the question? From a given substrate, what is the best organometallic reagent and the best transition metal to form a C-C bond by using a cross-coupling reaction? The solution might be found in these two books. * Organozinc reagents are used in cross-coupling reactions and have better chemoselectivity and functional group tolerance than Grignard reagents. * Catalysis of organozinc reagents using various metals for C-C bond formation is discussed. Cover Half Title Also of Interest Organozinc Derivatives and Transition Metal Catalysts: Formation of C-C Bonds by Cross-coupling Copyright Dedication Contents Preface 1. Organozinc reagents and palladium 1.1 Introduction 1.2 Discovery, early times and examples 1.3 Mechanistic insights 1.3.1 Rate determining step 1.3.2 Role of additives 1.3.3 Bimetallic interactions 1.3.4 Homocoupling undesirable pathways 1.3.5 β-hydride undesirable pathways 1.4 Remarkable ligands 1.4.1 Activation of strong C-X bonds: The quest for electron-rich ligands 1.4.2 Bypassing the hydride β-elimination 1.5 Applications 1.5.1 Arylzinc reagents 1.5.1.1 With aryl electrophiles 1.5.1.2 With vinyl electrophiles 1.5.1.3 Alkyl electrophiles 1.5.2 Vinylzinc reagents 1.5.2.1 With aryl electrophiles 1.5.2.2 With vinyl electrophiles 1.5.2.3 With alkyl electrophiles 1.5.3 Alkylzinc reagents 1.5.3.1 With aryl electrophiles 1.5.3.2 With vinyl electrophiles 1.5.3.3 With alkyl electrophiles 1.5.4 Alkynylzinc 1.5.4.1 With aryl electrophiles 1.5.4.2 With vinyl electrophiles 1.5.4.3 With alkyl electrophiles 1.5.4.4 With alkynyl electrophiles 1.6 Development of high-scale cross-coupling processes in modern organic synthesis 1.6.1 Addressing the question of palladium contamination 1.6.2 Toward easily scalable processes: Cross-couplings and flow chemistry 1.6.3 Green and sustainable Negishi cross-coupling in aqueous solvents 1.7 Synthesis of complex targets 1.7.1 Other applications of Pd-catalyzed Negishi couplings in total synthesis 1.7.2 Toward functionalization of highly sensitive targets 1.7.3 Applications in radiolabeling chemistry 1.8 Summary and conclusion References 2. Organozinc reagents and nickel 2.1 Introduction 2.2 Cross-coupling reactions of arylzinc reagents 2.2.1 With aryl derivatives 2.2.1.1 With aryl chlorides and bromides 2.2.1.2 With aryl fluorides 2.2.1.3 With phenol esters 2.2.1.3.1 With aryl pivalates 2.2.1.3.2 With aryl triflates 2.2.1.4 With aryl ethers 2.2.1.5 With aryltrimethylammonium iodides and triflates 2.2.1.6 With arylthioethers 2.2.1.7 With arylsulfonium salts 2.2.1.8 With arylmethylsulfoxides 2.2.2 With alkenyl derivatives 2.2.2.1 With enol ethers 2.2.2.1.1 With vinyl pivalates 2.2.2.1.2 With vinyl triflates 2.2.2.1.3 With vinyl phosphates 2.2.2.2 With sulfonium salts 2.2.3 With alkynyl derivatives 2.2.4 With alkyl derivatives 2.2.4.1 With secondary alkyl halides 2.2.4.1.1 With CF3-substituted secondary alkyl halides 2.2.4.1.2 With α-haloamides 2.2.4.1.3 With α-bromo alkylnitriles 2.2.4.2 With secondary benzyl mesylates 2.2.4.3 With allyl methyl ethers 2.2.4.4 With propargylic carbonates 2.2.4.5 With thiocarbamates 2.2.4.6 With trialkylsulfonium salts 2.2.4.7 With aliphatic carboxylic acids 2.2.4.8 With alkylsulfones 2.3 Coupling reactions of alkenylzinc reagents 2.3.1 With alkyl derivatives 2.3.1.1 With α-bromonitriles 2.3.1.2 With activated esters 2.4 Coupling reactions of alkynylzinc reagents 2.4.1 With aryl derivatives 2.4.2 With alkenyl derivatives 2.4.2.1 With alkenyl triflates 2.4.2.2 With alkenyl sulfonium salts 2.4.3 With alkyl derivatives 2.4.3.1 With N-hydroxyphthalimide aliphatic esters 2.5 Coupling reactions of alkylzinc reagents 2.5.1 With aryl derivatives 2.5.1.1 With aryl halides 2.5.1.2 With aryl fluorides 2.5.1.3 With aryl triflates 2.5.1.4 With phenol esters 2.5.1.5 With aryl ethers 2.5.1.6 With aryl thiomethylethers 2.5.1.7 With aryl trimethylammonium iodides 2.5.2 With alkenyl derivatives 2.5.2.1 With α-oxy-vinylsulfones 2.5.2.2 With alkenyl sulfoximines 2.5.3 With alkyl derivatives 2.5.3.1 With primary alkyl halides and alkylorganozinc species 2.5.3.2 With secondary alkyl halides 2.5.3.3 With propargyl bromides 2.5.3.4 With α-halosugars 2.5.3.5 With benzylic ethers and esters 2.5.3.6 With alkylpyridinium salts 2.5.4 With carboxylic acids 2.5.4.1 From alkyl carboxylic acid 2.5.4.2 From α-amino and α-acetoxyacids 2.5.4.3 From cyclobutane carboxylic acid 2.5.5 With N-tosylaziridines 2.5.6 Miscellaenous reactions 2.6 Conclusion References 3. Organozinc reagents and iron 3.1 Introduction 3.2 Cross-coupling reactions of alkylzinc reagents 3.2.1 With acyl chlorides 3.3 Cross-coupling reactions of arylzinc reagents 3.3.1 With aryl derivatives 3.3.2 With alkyl derivatives 3.3.3 With allyl and propargyl derivatives 3.3.4 With benzyl halides 3.4 Cross-coupling reactions of alkenylzinc reagents 3.4.1 With alkyl halides 3.5 Cross-coupling reactions of alkynylzinc reagents 3.5.1 With aryl halides 3.6 C-H bond activation 3.6.1 Iron-catalyzed arylation of C(sp2)-H bonds 3.6.2 Iron-catalyzed alkylation of C(sp2)-H bonds 3.6.3 Iron-catalyzed arylation of C(sp3)-H bonds 3.6.4 Iron-catalyzed alkylation of C(sp3)-H bonds 3.6.5 Iron-catalyzed addition of C(sp2)-H bonds to alkynes, alkenes and allenes 3.7 Mechanistic considerations 3.8 Conclusion References 4. Organozinc reagents and cobalt 4.1 Introduction 4.2 Formation of arylzinc reagents 4.3 Coupling reactions of arylzinc reagents 4.3.1 With aryl halides, heteroaryl halides and vinyl halides 4.3.2 With alkyl halides 4.3.3 With alkynyl halides 4.3.4 With acyl halides 4.3.5 With nitriles 4.3.6 With N-hydroxyphtalimide esters 4.4 Coupling reactions of alkenylzinc and alkynylzinc reagents 4.5 Coupling reactions of allylzinc reagents 4.6 Coupling reactions of alkylzinc reagents 4.6.1 With aryl and heteroaryl halides 4.6.2 With allyl and vinyl halides 4.6.3 With alkyl halides 4.6.4 With acyl chlorides 4.7 Multicomponent reactions 4.8 Conclusion References 5. Organozinc reagents and copper 5.1 Introduction 5.2 Coupling reactions of (hetero)arylzinc reagents 5.2.1 With (hetero)aryl halides 5.2.2 With acyl chlorides 5.2.3 With carbon dioxide 5.2.4 With allyl bromides 5.2.5 With a trifluoromethyl group using Togni’s reagent 5.3 Coupling reactions of alkenylzinc reagents 5.4 Coupling reactions of alkynylzinc reagents 5.5 Coupling reactions of alkylzinc reagents 5.5.1 With aryl and heteroaryl halides 5.5.2 With vinyl halides and vinyl pseudohalides 5.5.3 Coupling with acyl chlorides 5.5.4 With allyl halides 5.5.5 With propargyl pseudohalides 5.5.6 With α-halogeno carbonyl derivatives 5.5.7 Oxydative homocoupling of dialkylzinc reagents 5.6 Coupling of perfluoroalkylzinc reagents 5.6.1 With (hetero)aryl halides 5.6.1.1 Introduction of CF3 and perfluoroalkyl chains 5.6.1.2 Introduction of the CF2H moiety 5.6.1.3 Introduction of the -CF2P(O)(OR)2 moiety 5.6.2 With vinyl iodides and β-nitrostyrenes 5.6.3 With acyl chlorides 5.6.4 With bromoalkynes 5.6.5 With allyl halides 5.6.6 With propargyl halides 5.6.7 With alkyl halides 5.7 Conclusion References List of contributors Index