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 sulflides, 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.
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