Cross-Coupling Reactions of Persistent Tertiary Carbon Radicals

Abstract

Abstract The scope of cross-coupling reactions using tertiary carbon-centered radicals has expanded rapidly over the past decade. In this review, we outline the development of the cross-coupling reactions that involve persistent tertiary carbon-centered radicals as a powerful toolbox to synthesize molecules containing quaternary carbon(s) and/or tetra-substituted carbon(s). In particular, we focus on persistent tertiary carbon-centered radicals derived from carbonyl- or related compounds. We first describe the historical background and structural characterization of these radicals, and their reactivity/selectivity relationships. We then present selected recent examples of cross-coupling reactions involving tertiary carbon-centered radicals, categorized according to the originally proposed reaction mechanism, to showcase their versatile synthetic utility for structural diversification of small molecules.