Ligand-Controlled Divergent Cross-Coupling Involving Organosilicon Compounds for Thioether and Thioester Synthesis

A divergent cross-coupling for both thioether and thioester construction from organosilicon compounds has been developed. Predominant selectivity for Hiyama-type coupling and Cl insertion reaction was achieved under the guidance of ligands. Thioether was obtained under ligand-free conditions in which disulfide generated from homocoupling could be prevented. Meanwhile, application of bidentate phosphine ligands under carbon monoxide atmosphere (CO balloon) afforded the thioester with little decomposition, which was revealed through interval NMR tracking.