Visible-Light-Catalyzed Phosphorylation of Alkenes Enabled by Oxime Ether Reagents

Existing photocatalytic alkene phosphorylation relies on oxime ester-based phosphorus radical precursors, while conventional oxime ethers are severely limited by their inert N-O bond cleavage under photochemical conditions, restricting their synthetic utility. To overcome this bottleneck, we rationally designed and synthesized a novel class of photocleavable oxime ether phosphorylating reagents by incorporating a labile C-Br bond as an exogenous radical initiation site. This tailored molecular design successfully circumvents the intrinsic photoinertness of classic oxime ethers and enables efficient visible-light-driven generation of key phosphoryl radicals. The mild protocol affords structurally diversified alkenyl phosphates with broad substrate tolerance, scalable synthetic capability, and excellent functional group compatibility. This work establishes a distinctive radical phosphorylation strategy and greatly expands the applicability of oxime ether scaffolds in photoredox catalysis and organophosphorus synthesis.