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

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)─C(sp) 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.