β-Substituted Styrenes in Heteroaryl-Directed Hydroalkylative Cross-Couplings: Regio-, Diastereo-, and Enantioselective Formation of β-Stereogenic Tertiary Alcohols.

Under iridium-catalyzed conditions, 2-azaaryl-substituted secondary alcohols undergo C(sp3)-H addition reactions to β-substituted styrenes to provide alkylated tertiary alcohols. The processes occur with high regio-, diastereo-, and enantioselectivity and offer unusual examples of 1,2-disubstituted styrenes engaging in α-selective and stereocontrolled C-H addition reactions.