Site- and Enantioselective Homobenzylic C(sp 3 )-H Borylation via Dehydrogenation of Alkyl Chains.

A one-pot, dehydrogenation-based Ir/Co/Cu triple catalysis has been developed for formal asymmetric borylation of homobenzylic C(sp 3 )-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.