Decarboxylative Acylation of Carboxylic Acids: Reaction Investigation and Mechanistic Study

Ketones serve as one of the most critical building blocks in organic synthesis, involving numerous functional group transformations. Herein, we rep ort an unprecedented photoredox-nickel metallap hotoredox-catalyzed decarboxylative acylation of common aliphatic acids with readily available aromatic and aliphatic thioesters. A wide range of structurally diverse asymmetrical aryl alkyl and dialkyl ketones have been constructed in yields of up to 98% with this strategy. The protocol has excellent reaction selectivity and functional group compatibility, representing a significant step forward in ketone synthesis. The one-pot decarboxylative acylation at the gram scale from two different carbox- synthesis of complex ketones shows its synthetic robustness. Both mechanistic experiments and density functional theory (DFT) calculations suggest that the decarboxylative acylation reaction operates via an underdeveloped Ni( I)-Ni(II)-Ni( I)Ni(III)-Ni(I) catalytic cycle. [GRAPHICS] .