Copper-Catalyzed Asymmetric Functionalization of Vinyl Radicals for the Access to Vinylarene Atropisomers

摘要

A novel asymmetric radical strategy for the straightforwardsynthesisof atropisomerically chiral vinyl arenes has been established herein,proceeding through copper-catalyzed atroposelective cyanation/azidationof aryl-substituted vinyl radicals. Critical to the success of theradical relay process is the atroposelective capture of the highlyreactive vinyl radicals with chiral L*Cu(II) cyanide or azide species.Moreover, these axially chiral vinylarene products can be easily transformedinto atropisomerically enriched amides and amines, enantiomericallyenriched benzyl nitriles via an axis-to-center chirality transferprocess, and an atropisomerically pure organocatalyst for the chemo-,diastereo-, and enantioselective (4 + 2) cyclization reaction.