Heteroaryl-Directed Iridium-Catalyzed Enantioselective C-H Alkenylations of Secondary Alcohols.

Under iridium-catalyzed conditions, 2-aza-aryl-substituted secondary alcohols undergo C(sp)-H addition reactions to alkynes to provide alkenylated tertiary alcohols. The processes occur with very high regio- and enantioselectivity. An analogous addition to styrene is shown to provide a prototype C(sp)-H alkylation process. A mechanism based on directed aza-enolization of the reactant alcohol is proposed.