Ligand-enabled, Ni-catalyzed dicarbofunctionalization of alkenyl alcohols

Abstract

An alcohol-directed 1,2-dicarbofunctionalization of alkenyl alcohols has been realized with aryl/alkenyl boronic acids and alkyl halides as the coupling partners. This reaction was enabled by a commercially available bulky 3-amyl β-diketone (Amacac) ligand, which enhances the reactivity and suppresses many competitive processes. With alcohol as a weak native directing group, this protocol delivers 1,2-arylalkylated and 1,2-alkenylalkylated alcohols with high efficiency, high regioselectivities, a broad substrate scope, and exceptional functional group tolerance. Notably, this methodology facilitates the modular synthesis of biologically active compounds and key alcohol-containing synthetic intermediates. Preliminary mechanistic studies shed light on the neutral coordination of alcohol functionality to nickel catalysts and the origin of regioselectivity.