Iridium Complexes as Efficient Catalysts for Construction of α‐Substituted Ketones via Hydrogen Borrowing of Alcohols in Water

Abstract Ketones are of great importance in synthesis, biology, and pharmaceuticals. This paper reports an iridium complexes‐catalyzed cross‐coupling of alcohols via hydrogen borrowing, affording a series of α ‐alkylated ketones in high yield (86 %–95 %) and chemoselectivities (>99 : 1). This methodology has the advantages of low catalyst loading (0.1 mol%) and environmentally benign water as the solvent. Studies have shown the amount of base has a great impact on chemoselectivities. Meanwhile, deuteration experiments show water plays an important role in accelerating the reduction of the unsaturated ketones intermediates. Remarkably, a gram‐scale experiment demonstrates this methodology of iridium‐catalyzed cross‐coupling of alcohols has potential application in the practical synthesis of α ‐alkylated ketones.