Alcohol Activation by Benzodithiolylium for Deoxygenative Alkylation Driven by Photocatalytic Energy Transfer

Abstract The 1,3‐benzodithiolylium (BDT) cation was identified as an efficient hydroxyl‐activating reagent for the photocatalytic deoxygenative radical functionalization of alcohols in the absence of any electron transfer process. A series of unprecedented photocatalytic energy transfer (EnT)‐driven deoxygenative radical coupling reactions of alcohols with bifunctional oxime carbonates have been developed based on the activation by BDT. Nickel‐catalyzed radical sorting followed by C(sp 3 )─C(sp 3 ) bond construction facilitates the heteroselective cross‐coupling of two distinct alkyl radicals originating from parallel radical relays. These reactions allow the versatile synthesis of diverse nitrogen‐containing molecules, including amino acid derivatives, imines, nitriles, and pyrrolines, by using ubiquitous alcohols as regiodefined alkyl building blocks.