Elemental‐Sulfur‐Enabled Divergent Synthesis of Disulfides, Diselenides, and Polythiophenes from β‐CF 3 ‐1,3‐Enynes

Divergent synthesis for precise constructions of cyclic unsymmetrical diaryl disulfides or diselenides and polythiophenes from CF 3 ‐containing 1,3‐enynes and S 8 was developed when the ortho group is F, Cl, Br, and NO 2 on aromatic rings. Meanwhile, disulfides (diselenides) were also quickly constructed when the ortho group is H. These transformations undergo cascade thiophene construction/selective C3‐position thiolation process, featuring simple operations, divergent synthesis, broad substrate scope, readily available starting materials, and valuable products. A novel plausible radical annulation process was proposed and validated by DFT calculations for the first time. A series of derivatizations about the thiophene (TBT) and disulfides were also well‐represented.