Transition-Metal-Free Cleavage of C–C Triple Bonds in Aromatic Alkynes with S₈ and Amides Leading to Aryl Thioamides

A novel transition-metal-free cleavage reaction of C–C triple bonds in aromatic alkynes with S₈ and amides furnishes aryl thioamides in moderate to excellent yields. The remarkable features of this thioamidation include the metal-free cleavage of C–C triple bond, mild reaction conditions, as well as wide substrate scope that is particularly compatible with some internal aromatic alkynes and acetamides

Asymmetric Synthesis of P‑Stereogenic Phosphinic Amides via Pd(0)-Catalyzed Enantioselective Intramolecular C–H Arylation

The palladium-catalyzed enantioselective intramolecular C–H arylation of <i>N</i>-(2-haloaryl)-<i>P,P</i>-diphenylphosphinic amides furnishes <i>P</i>-stereogenic phosphine oxide derivatives in 61–99% yield with 88–97% ee. The catalyst generated in situ from a TADDOL-derived phosphoramide ligand and Pd­(dba)₂ is optimum in terms of yield and enantioselectivities