Site- and Enantioselective Homobenzylic C(sp3)-H Borylation via Dehydrogenation of Alkyl Chains.

Abstract

A one-pot, dehydrogenation-based Ir/Co/Cu triple catalysis has been developed for formal asymmetric borylation of homobenzylic C(sp3)-H bonds, furnishing enantioenriched organoboronates with a β-stereocenter directly from simple arylalkanes. Mechanistic studies indicate that the Ir catalyst is responsible for dehydrogenation of arylalkanes to 1-arylalkenes, followed by Cu-catalyzed regio- and enantioselective protoboration of (E)-arylalkenes; the introduction of Co-catalyzed stereoisomerization of the (Z)-alkenes to (E)-isomers was found to have a beneficial effect on the productivity and enantioselectivity.