Alkoxy Diazomethylation of Alkenes by Photoredox-Catalyzed Oxidative Radical-Polar Crossover

Herein, we present the discovery and development of the first photoredox-catalyzed alkoxy diazomethylation of alkenes with hypervalent iodine reagents and alcohols. This multicomponent process represents a new disconnection approach to diazo compounds and is featured by a broad scope, mild reaction conditions, and excellent selectivity. Key to the process was the generation of diazomethyl radicals, which engaged alkenes and alcohols in an inter- and intramolecular fashion by a photoredox-catalyzed oxidative radical–polar crossover leading to unexplored β-alkoxydiazo compounds. The synthetic utility of such diazo compounds was demonstrated with a series of transformations involving C–H, N–H, and O–H insertions as well as in the construction of complex sp³-rich heterocycles.