Catalytic Alkyne Hydrothiolation with Alkanethiols using Wilkinson's Catalyst

Abstract

We recently discovered that Wilkinson's catalyst (ClRh(PPh3)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.