A divergent
cross-coupling for both thioether and thioester construction
from organosilicon compounds has been developed. Predominant selectivity
for Hiyama-type coupling and C1 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
