Metallaphotoredox-Catalyzed Deconstructive Acylation of Cycloalkanols with Carboxylic Acids to Access Remote Diketones.

Herein, we report a photoredox/nickel dual-catalyzed strategy that merges the deconstruction of cyclic alcohols with low-valent metal oxidative addition, enabling the direct use of carboxylic acids as acyl donors for the programmable synthesis of 1,n-diketones, ranging from 1,4- to 1,7-diketones. The method accommodates both aliphatic and aromatic acids, and the resulting 1,n-diketones serve as versatile handles for downstream heterocyclization. Its synthetic utility is demonstrated by the late-stage functionalization of natural products and the efficient construction of bioactive molecules.