Subtle changes in molecular structure can lead to profound changes in molecular function. However, even minor structural refinements can require the complete resynthesis of a target molecule, adding time and cost to molecular design campaigns1. Recently, editing methods have emerged targeting subtle molecular perturbations, including atomic substitution, stereocentre inversion and functional group repositioning2. These precision tools hold the potential to streamline the optimization of molecular function by fine-tuning molecular structure. Here we report an editing method that enables the migration of common alcohol functional groups to proximal sites with predictable stereo- and regiochemical outcomes. The reaction proceeds through a 1,2-acyloxy radical migration step under reversible H atom transfer catalysis conditions promoted by the excited-state decatungstate polyanion. Proximity effects arising from non-covalent interactions between substrate and reagent enable efficient radical formation at polarity-mismatched positions. Application of this tool at a late synthetic stage allows for the precise repositioning of alcohol functional groups, whereas integration with common alcohol group installation methods provides new synthetic strategies to access challenging oxygenation patterns.
