Photoinduced Intermolecular Hydroamination and Hydroetherification of Electron‐Rich Alkenes With Low Catalyst Loadings

A photochemical method based on visible‐light irradiation (blue LEDs/sunlight) has been developed for the intermolecular hydroamination and hydroetherification of electron‐rich alkenes. This photochemical method is compatible with a wide range of azoles and electron‐rich alkenes, such as vinyl ethers, vinyl sulfides and enamides, and is performed with low concentrations of photocatalyst (1000 ppm). Comprehensive mechanistic studies indicate that this process is initiated by the formation of an active radical cation intermediate through single electron oxidation of azole, which is mediated by excited Acr‐Mes + BF 4 − .