Abstract Alcohols are ubiquitous in natural products and serve as versatile synthetic handles; however, the relocation of a hydroxyl group to an adjacent C–H site remains an underdeveloped yet highly valuable transformation. Herein, we report a photocatalytic 1,2-translocation of oxamoyl-protected alcohols enabled by a reversible C–H sampling strategy. Utilizing a cooperative hydrogen atom transfer catalytic system, a range of carbon radicals are transiently generated, while the β-acyloxy alkyl radical selectively undergoes a 1,2-acyloxy shift to afford the rearranged product. The oxamoyl protecting group exhibits superior performance, likely accelerating the radical-acyloxy rearrangement while simultaneously enhancing β-HAA probability. This redox-neutral methodology accommodates a broad substrate scope with predictable regio- and stereoselectivity, including the late-stage modification of complex bioactive molecules. Beyond facile hydrolytic removal, the oxamoyloxy handle can be directly converted into alkyl iodides, providing an additional entry point for further diverse functionalizations.
Su et al. (2026) studied this question.