Access to Hindered Alkyl Aryl Ethers via Radical–Polar Crossover C(sp ³ )–O Coupling Enabled by Dual Organosulfur/Photoredox Catalysis

A dual organosulfur/photoredox catalytic method for radical-polar crossover (RPC) C(sp³)-O coupling between phenols and alkyl radical precursors is reported. While prototypical photocatalytic systems are incompatible with phenols due to their redox non-innocent behavior and low nucleophilicity, we show that incorporation of an organosulfur electron-shuttle catalyst enables the phenols to serve as competent <i>O</i>-nucleophiles in RPC chemistry. This system operates efficiently at sterically demanding sites with only stoichiometric phenol, thus providing an efficient route to hindered alkyl aryl ethers that are difficult to access using current cross-coupling methods.