LiAlH₄‐Induced Thia‐Aza‐Payne Rearrangement of Functionalized 2‐(Thiocyanatomethyl)aziridines into 2‐(Aminomethyl)thiiranes as an Entry to 5‐(Chloromethyl)thiazolidin‐2‐ones

Abstract

Nonactivated 2‐(thiocyanatomethyl)aziridines with diverse substitution patterns were deployed as substrates to effect a LiAlH4‐promoted thia‐aza‐Payne rearrangement to provide access to functionalized 2‐(aminomethyl)thiiranes in good to excellent yields (78–94 %). The developed strategy involved hydride reduction of the thiocyanato moiety followed by intramolecular aziridine ring opening. Subsequent exposure of the obtained 2‐(aminomethyl)episulfide intermediates to triphosgene resulted in the formation of 5‐(chloromethyl)thiazolidin‐2‐ones.