C–C Bond Formation by Cross-Coupling ☆ SP Nolan, University of St Andrews, St Andrews, UK O Navarro, University of Sussex, Brighton, UK ã 2013 Elsevier Inc. All rights reserved. Introduction 1 Cross-Coupling Reactions 2 Reactions with Organoboron Reagents: The Suzuki–Miyaura Reaction 2 New coupling partners 3 Palladacycle complexes as catalysts precursors 5 Catalytic systems composed of Pd(0) or Pd(II) derivatives and phosphines 5 Catalytic systems composed of Pd(0) or Pd(II) and N-heterocyclic carbenes 7 Ligandless systems 8 Systems in aqueous media 9 Supported and heterogeneous systems 9 Non-palladium-based systems 10 Reactions with Organostannane Reagents: The Migita–Kosugi–Stille Reaction 10 New coupling partners 10 Palladacycle complexes as catalysts precursors 12 Catalytic systems composed of Pd(0) or Pd(II) and phosphines 12 Catalytic systems composed of Pd(0) or Pd(II) and N-heterocyclic carbenes 13 Other systems 13 Reactions of Terminal Alkynes 13 The Sonogashira coupling reaction 13 Acetylene surrogates 15 The Cadiot–Chodkiewicz reaction 17 Reactions with Organomagnesium Reagents: The Kumada–Tamao–Corriu Reaction 17 Nickel-based systems 18 Iron-based systems 18 Palladium-based systems 19 Other systems 20 Reactions with Organosilicon Reagents: The Hiyama Reaction 20 Coupling of arylsilanes 21 Coupling of alkenylsilanes 22 Fluoride-free systems 23 Pd- or Ni-catalyzed Reactions with Organozinc Reagents: The Negishi Coupling 24 Arylzinc reagents 24 Alkenyl- and alkylzinc reagents 26 Closing Remarks 26 References 27 Introduction Cross-coupling reactions represent a class of synthetic transformations that involve the combination of an organometallic reagent (that has a main group metal atom in most of cases) with an organic electrophile in the presence of groups 8–10 metal catalysts to achieve a C–C, C–H, C–N, C–O, C–S, C–P, or C–M bond formation. 1 Since the initial discoveries in this area in the early 1970s by Kumada, Kochi, Corriu, and Murahashi, many organometallic reagents, such as organoboron, organotin, organosilicon, and organozinc have proved to be useful for cross-coupling reactions. Many different types of electrophiles and metal complexes have been successfully employed in these reactions, resulting in a plethora of synthetic methods for molecular assemblies. For this reason, cross-coupling reactions have been used in numerous organic synthetic applications ranging from polymers and liquid crystals to pharmaceuticals and natural products. A general catalytic cycle for cross-coupling reactions is depicted in Scheme 1. In general, the reaction occurs by a sequence of oxidative addition–transmetallation–reductive elimination. The characteristics of both the transition metal and the main group metal reagent, in addition to effects associated with other reaction conditions, will affect the catalytic performance. The oxidative ☆ Change History: June 2013. O Navarro updated captions for figures, schemes, tables and references. Reference Module in Chemistry, Molecular Sciences and Chemical Engineering http://dx.doi.org/10.1016/B978-0-12-409547-2.03966-4 1