Site-SelectiveCopper–<i>N</i>‑HeterocyclicCarbene-Catalyzed C(sp²)–C(sp) Cross-Coupling ofAryl Thianthrenium Salts

This work demonstrates Cu–NHC (NHC = <i>N</i>-heterocyclic carbene) catalyzed alkynylation of aryl thianthrenium salts via thiazol-2-ylidene ligands, achieving a Pd-free Sonogashira coupling with broad substrate compatibility and functional group tolerance. Late-stage pharmaceutical alkynylation and rare alkynylative C–H functionalization/ring-opening pathways are enabled. Thiazol-2-ylidenes, featuring a “half-umbrella”-shaped geometry, exhibit superior catalytic performance over traditional imidazol-2-ylidenes, underscoring their unique ligand efficacy. Cu–NHC catalysis enables the use of aryl thianthrenium salts as versatile electrophiles for diverse cross-couplings under mild conditions.