Light/copper catalysis in 1,2-alkylarylation of allylic alcohols with sulfonium salts involving radical 1,2-aryl migrations

A visible-light-induced copper catalysis radical relay reaction of <i>a</i>,<i>a</i>-disubstituted allylic alcohols with sulfonium salts is described. The established protocol provides facile access to distal keto thioether derivatives <i>via</i> radical C-S bond cleavage and a 1,2-aryl migration relay strategy. A synthetic application of the product was achieved through a simple reduction or oxidation for the preparation of value-added compounds, including alcohols, sulfoxide, and sulfone-substituted thioether derivatives. Additionally, our methodology provided the direct assembly of keto-containing thioether molecules and displayed excellent chemo- and regio-selectivity, broad substrate scope, and mild reaction conditions.