Ligand-modulated regiodivergent alkenylboration of allylarenes: Reaction development and mechanistic study

Abstract

Chain-walking has emerged as a promising strategy in organic synthetic methodology, but achieving site-selectivity in reactions involving competition among multiple potential positions remains a challenge. In this study, we presented a novel approach to ligand-modulated, nickel-catalyzed regiodivergent alkenylboration of allylarenes. Our method allows for highly chemoselective preparation of two classes of structurally different alkenyl boronates from the same starting by simply switching the ligand. Mechanistic investigations involving experiments and calculations suggest that the ligand-modulating regiodivergence arises from either regioselective β-H elimination or oxidative addition with organic halides. Our findings offer valuable insight into addressing site-selective issues in chain-walking reactions with multiple thermodynamically stable factors.