Alkoxy Diazomethylation of Alkenes by Photoredox-Catalyzed Oxidative Radical-Polar Crossover
Qiyuan He, Quan Zhang, Alessa B. Rolka, Marcos G. Suero
Abstract
High Resolution Image Download MS PowerPoint Slide 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 sp 3 -rich heterocycles.