A robust strategy for the hydrothiolation of heterocycloalkynes with in situ generated dithiocarbamic acids, "Strain-Promoted diThiocarbamic acid-Alkyne Click" (SPTAC), was developed and successfully extended to diverse cycloalkynes and a wide range of amines and their hydrochlorides, affording hydrothiolation adducts in high to excellent yields. DFT calculations revealed a concerted pseudopericyclic mechanism of SPTAC. The thiol-yne click transformation provides a versatile platform for the con