Direct couplings of secondary alcohols with primary alkenyl alcohols to α-alkylated ketones via a tandem transfer hydrogenation/hydrogen autotransfer process catalyzed by a metal-ligand bifunctional iridium catalyst

• New strategy for the synthesis of α -alkylated ketones based on hydrogen autotranser process. • Primary alkenyl alcohols were utilized as hydrogen sources and alkylating agents. • Functional groups in bpy ligand are crucial for transfer hydrogenation/hydrogen autotransfer process. • The catalytic system was applied to the synthesis of a biologically active compound. A new strategy for the synthesis of α -alkylated ketones from secondary alcohols and primary alkenyl alcohols via a tandem transfer hydrogenation/hydrogen autotransfer process was proposed and successfully accomplished. Mechanistic experiments supported that functional groups in bpy ligand are crucial for the transfer hydrogenation and hydrogen autotransfer process. Furthermore, the utilization of the present catalytic system for the gram-scale synthesis of a biologically active compound was presented.