A method for the catalytic enantioselective diarylation of alkenes is presented. The method allowed for the synthesis of highly enantioenriched 2,3-dihydrobenzofurans and indolines containing molecules from readily available substrates. Furthermore, this method allowed for the enantioselective synthesis of quaternary carbons. Based on mechanism studies, the process likely functions by enantioselective insertion of an alkene into an Ar-CuBenzP* complex to generate a Csp(3)-Cu complex. Capture of this intermediate with an ArX led to formation of the desired product.