Allylation of (Hetero)aryl Thioethers and Related Compounds With 2‐Alkenylaziridines

We report a transition‐metal‐free, atom‐economical, and highly selective aryl allylation method of (hetero)aryl thioethers and aryl selenoethers with 2‐alkenylaziridines in 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) under mild conditions. Adjusting the reactant ratio and reaction temperature enables selective access to either ortho ‐allylated or 2,6‐bis‐allylated aryl thioethers and aryl selenoethers. Benzo[ b ]thiophenes and dibenzo[ b , d ]thiophene also undergo allylation under the same conditions. The method accommodates a broad range of substrates, tolerates diverse functional groups, and exhibits good regioselectivity and Z / E selectivity.