Stereoselective Construction and Skeletal Reorganization of Conjugated Enynes

Skeletal reorganization reactions are highly efficient tools for constructing complex heterocycles and diverse molecular architectures, with significant value in organic synthesis. This study reports a unique 6-exo-dig cyclization of conjugated enynes accompanied by sulfonyl migration, which expands the scope of cyclization and skeletal reorganization processes. The enyne substrates are readily prepared via direct alkenyl C–H bond alkynylation, simplifying the synthetic pathway while enhancing efficiency. Moreover, mechanistic investigations of the reaction pathway and studies of the optical properties of the final products demonstrate their potential applications in photofunctional materials.