Suzuki–Miyaura Cross‐Coupling

The Suzuki–Miyaura cross coupling reaction uses a metal catalyst to create carbon–carbon bonds from organoboron reagents and organo(pseudo)halides. By careful adjustment of the ligand system, solvents, and other additives, this reaction can couple a diverse range of sp‐, sp 2 ‐, and sp 3 ‐hybridized organoboron and organo(pseudo)halide reactants. The Suzuki–Miyaura cross coupling reaction has become preeminent in both small‐ and large‐scale synthesis owing to its mild reaction conditions, predictable stereochemical outcomes, chemoselectivity, functional‐group compatibility, and use of relatively non‐toxic and air‐stable starting materials. This chapter describes the theoretical and practical aspects of the palladium‐catalyzed Suzuki–Miyaura cross‐coupling reaction. A broad overview of the reaction mechanism and scope is described, with selected examples of how mechanistic insights have enabled progress in the development of this coupling reaction. Examples include early reaction discovery as well as modern applications in synthesis using a diverse array of organoboron and organo(pseudo)halide reactants, and on scales that range from milligram to multi‐kilogram. Tabular surveys are organized by the structure of the transferable group attached to boron as the primary rubric (alkyl, alkenyl, aryl, alkynyl, then heterocyclic), with the structure of the electrophile as the secondary rubric. Selected literature is covered from the seminal paper in 1979 to mid‐2018.