Intermolecular Trapping of Alkoxyl Radicals with Alkenes: A New Route to Ether Synthesis

Alkoxyl radicals are highly reactive species which rapidly react by hydrogen atom transfer (HAT) or beta-fragmentation to afford a carbon-centered radical. We discuss herein how these RO center dot radicals can be efficiently trapped in an intermolecular manner by styrene derivatives when they are generated by photoredox catalysis from the corresponding N-alkoxypyridinium salts. This allows for the synthesis of valuable ethers with complete anti-Markovnikov regioselectivity.