AbstractUnlike aromatic allenes, the hydrothiolation of aliphatic allenes has proven challenging for previously developed catalysts. Herein, a 3‐iminophosphine supported palladium catalyst is shown to be highly effective for the double hydrothiolation of aliphatic allenes, producing dithioacetals in a regioselective and atom‐efficient manner. The utility of this methodology is demonstrated for twelve new dithioacetals formed from aliphatic allenes and aryl thiols and isolated in moderate to excellent yields in all cases.
