Abstract: | For the first time a mild and efficient procedure has been developed for the C‐3 selective ring opening, under biomimetic conditions, of 2,3‐aziridino alcohols and their derivatives with nucleophiles such as aromatic thiols and amines catalyzed by β‐cyclodextrin in water at room temperature to afford the corresponding β‐amino sulfides and diamines with high regioselectivity in impressive yields. The use of cyclodextrin precludes the use of either acid or base and the catalyst can be recovered and reused. |