Bi(III)-CatalyzedNewman–Kwart Rearrangementfor Synthesizing <i>S</i>‑Heteroaryl Thiocarbamates

Newman–Kwart rearrangement (NKR) is a useful method for synthesizing <i>S</i>-aryl thiocarbamates from <i>O</i>-aryl thiocarbamates. Harsh temperature conditions are required, however, leading to substrate degradation and side reactions. Moreover, reactions using heteroaromatic substrates are quite rare. Herein, we report Bi(OTf)₃-catalyzed NKR using heteroaromatic substrates under ambient temperature conditions. The reaction extended to not only aza-arene substrates but also thiophene substrates.