7.18 Addition Reactions with Formation of Carbon–Carbon Bonds: (v) The Oxidative Heck Reaction

Abstract

The Heck reaction, generally defined as the substitution of a vinylic hydrogen with an aryl, vinyl, or benzyl group, is widely regarded as one of the premier synthetic tools for the construction of new C–C bonds. The oxidative Heck reaction, which commences with the generation of the key arylpalladium species under palladium(II) catalysis, has emerged as a powerful alternative to the palladium(0)-catalyzed Mizoroki−Heck reaction over the past decade. This chapter gives an overview of the various olefin and aryl/vinyl substrate classes that have been utilized in this reaction. The material is organized according to the reaction type (inter- or intramolecular), the electronic nature of the olefin (electron-poor, electron-rich, or neutral), and the olefin coupling partner. Special emphasis is given to some of the more recent advances in this area and, where applicable, a critical review of the most synthetically useful methods is presented.