Alkyne hydrothiolation catalyzed by a dichlorobis(aminophosphine) complex of palladium: selective formation of cis-configured vinyl thioethers.

Cis all round: Dichlorobis[1-(dicyclohexylphosphanyl)piperidine]palladium, [(P{(NC(5)H(10))(C(6)H(11))(2)})(2)Pd(Cl)(2)], is a highly efficient alkyne hydrothiolation catalyst and the first generally applicable system that selectively generates cis-configured anti-Markovnikov adducts in excellent yields within only a few minutes at 120 °C in the presence of only 0.05 mol % of the catalyst (see scheme).