Solvent‐Controlled Selective Selenylation and Sulfonylation of 1,7‐Dienes With Selenosulfonates for Divergent Synthesis of Seleno‐/Sulfonyl‐Benzoxepines

A metal-free selective selenylation and sulfonylation of 1,7-dienes with selenosulfonates for divergent synthesis of seleno-/sulfonyl-benzoxepines has been developed. This reaction was conducted under mild conditions without any catalysts, oxidants, or additives. The choice of solvent plays a crucial role in determining the formation of seleno-/sulfonyl-benzoxepines. Preliminary mechanistic studies suggest that both the selenylation and sulfonylation are accomplished through a selenyl radical and a sulfonyl radical cyclization process.