Alkoxyl Radicals Generated under Photoredox Catalysis: A Strategy for anti‐Markovnikov Alkoxylation Reactions.

Reported herein is a novel photoredox‐catalyzed approach for ether synthesis and it involves alkoxyl radicals generated from N‐alkoxypyridinium salts. A wide range of alkenes are smoothly difunctionalized in an anti‐Markovnikov fashion, affording various functionalized alkyl alkyl ethers. Notably, this mild process tolerates a number of functional groups and is efficiently carried out under both batch and flow conditions. Importantly, electron paramagnetic resonance (EPR) experiments by spin trapping were carried out to characterize the radical intermediates involved in this radical/cationic process. Falling into a trap: Alkoxyl radicals generated under visible light photoredox catalysis from N‐alkoxypyridinium salts were efficiently trapped by alkenes in an intermolecular fashion under either batch or flow conditions. This alkoxylation strategy provides access to a wide variety of functionalized alkyl alkyl ethers by the difunctionalization of alkenes with perfect anti‐Markovnikov selectivity. [ABSTRACT FROM AUTHOR]