Metal‐Free and Visible Light‐Induced Difunctionalizations of α ‐CF 3 Styrenes with Aryl Diazonium Salts and Hetero Nucleophiles

Metal‐free, visible light‐induced difunctionalizations of α ‐CF 3 styrenes with aryl diazonium salts and various hetero nucleophiles (ROH, H 2 O, N 3 − and F − ) are described. This concise protocol provided easy access to the α ‐CF 3 tertiary alkyl ethers, alcohol and fluorides with good yields and excellent functional group tolerance. In addition, the four‐component “SO 2 ” insertion reaction also worked efficiently to produce the α ‐CF 3 , β ‐sulfonyl ethers in moderate to good yields. A radical‐polar crossover coupling pathway was proposed for the C−O bond formation.