Direct C–H Arylation of Aldehydes by Merging Photocatalyzed Hydrogen Atom Transfer with Palladium Catalysis

Abstract

Herein, we report that merging palladium catalysis with hydrogen atom transfer (HAT) photocatalysis enabled direct arylations and alkenylations of aldehyde C–H bonds, facilitating visible light-catalyzed construction of a variety of ketones. Tetrabutylammonium decatungstate and anthraquinone were found to act as synergistic HAT photocatalysts. Density functional theory calculations suggested a Pd0–PdII–PdIII–PdI–Pd0 pathway and revealed that regeneration of the Pd0 catalyst and the photocatalyst occurs simultaneously in the presence of KHCO3. This regeneration features a low energy barrier, promoting efficient coupling of the palladium catalytic cycle with the photocatalytic cycle. The work reported herein suggests great promise for further applications of HAT photocatalysis in palladium-catalyzed cross-coupling and C-H functionalization reactions to be successful.