Ligand-Controlled Regiodivergent Copper-Catalyzed Alkylboration of Unactivated Terminal Alkynes

Abstract

A ligand-controlled regiodivergent and stereospecific copper-catalyzed alkylboration of unactivated terminal alkynes has been developed. Anti-Markovnikov alkylboration products were obtained with dppbz as ligand; conversely, Markovnikov alkylboration products were obtained with DMAP as ligand. This reaction not only presents a direct route to construct a vinyl C(sp2)–C(sp3) bond but also provides an efficient way to synthesize both internal and external vinylboronic esters regiodivergently from a single unactivated terminal alkyne.