Hemin Catalyzed Dealkylative Intercepted [2, 3]‐Sigmatropic Rearrangement Reactions of Sulfonium Ylides with 2, 2, 2‐Trifluorodiazoethane

Abstract A dealkylative intercepted [2, 3]‐sigmatropic rearrangement reaction of allylic sulfides with 2, 2, 2‐trifluorodiazoethane (CF 3 CHN 2 ) is reported, the commercially available and biocompatible catalyst hemin was found to efficiently catalyze this transformation across a diverse set of allylic sulfides with in situ generated CF 3 CHN 2 , providing excellent yields (up to 99%) under mild condition without inert gas protection. In addition, CF 3 CHN 2 exhibited unique reactivity toward this process compared with other frequently used diazo reagents. This work expands the range of carbene‐mediated transformations catalyzed by hemin and introduces a concise and general strategy for exploiting new possibility of reactions concerning organosulfides. magnified image