C(sp 3 )‒H Activation of Alcohol for C(sp 3 )‒C(sp 3 ) Bond Formation via Heterogeneous Photocatalysis in Flow

Abstract C(sp 3 )‒H activation of alcohols enables creating new C─C bond while keeping hydroxyl group in a step and atom economic manner. Here, we disclose a protocol of coupling alcohols with alkenes for C(sp 3 )‒C(sp 3 ) bond formation via heterogeneous photocatalysis in flow. This protocol functions well with a broad scope of alcohols (primary and secondary alcohols) and alkenes with moderate to good yields. The heterogeneous photocatalysis in flow enables current methodology to be conducted even on gram scale, exhibiting great potential for industrial applications. Cleavage of α‐C(sp 3 )‒H of alcohol is induced by S • species on the surface of ZnIn 2 S 4 via hydrogen atom transfer (HAT), and this step was found to be involved in the rate‐determining step.