By employing enaminones and thiuram disulfides as starting materials, the frontiers of Newman-Kwart rearrangement have been expanded to the alkenyl system for the first time. In addition, instead of leading to the formation of simple carbamothioates, the rearrangement has led to the unprecedented construction of S-heteroaryls. Depending on the differences in the enaminone structure, the efficient synthesis of functionalized isothiazoles and thiophenes has been achieved.