Late-Stage C–H Diversifications with Ambiphilic α-Bromoboronates: Versatile Access to Transformable meta-Boroalkyl Scaffolds

Abstract

The ruthenium-catalyzed meta-C–H alkylation is an increasingly powerful strategy in the arena of remote C–H activation. Currently, the synthesis utility of this strategy is compromised owing to its relatively narrow substrate scope and the challenging diversification of the alkylation products. To address these issues, we herein report a modular ruthenium-catalyzed meta-C–H functionalization with readily available ambiphilic α-bromoboronates, providing expedient access to densely functionalized boronates. This remote activation was accomplished under exceedingly mild conditions, featuring high site-selectivity with ample substrate scope. The robustness was highlighted by the straightforward diversification of the thus-obtained alkylboronate esters, reflecting their transformative nature. Furthermore, the unprecedented installation of primary alkyl chains to the meta-position of arenes was thus realized. Our approach proved amenable for the late-stage functionalization of a diverse array of structurally complex, biorelevant molecules.