Catalytic Alkyne Hydrothiolation with Alkanethiols using Wilkinson's Catalyst

We recently discovered that Wilkinson's catalyst (ClRh(PPh 3 ) 3 ) is an excellent catalyst for alkyne hydrothiolation with alkanethiols to provide linear alkyl ( E )-vinyl sulfides, which are valuable synthetic intermediates and precursors to bioactive molecules. Deuterium-labeling studies indicate that the reaction proceeds by thiol oxidative addition, alkyne migratory insertion, and subsequent reductive elimination.