A novel catalyst‐free aminochlorination of alkenes was developed by the direct addition of alkenes to N‐chloro‐N‐fluorobenzenesulfonamide (CFBSA). The reaction produces 2‐chloro‐3‐fluoramino and 3‐chloro‐2‐fluoroamino adducts in 1,2‐dichloroethane under reflux and dichloromethane at room temperature, respectively, in a regioselective manner. The electronic and steric effects of the fluorine atom of CFBSA have proven to be crucial for the reactivity and regioselectivity. A variety of transformations have been achieved to form 2‐chloroenamines, chloroamines, aziridines and N‐phenylbenzenesulfonamides under different conditions. Notably, the N–F bond in the adducts formed could be a useful handle for further transformations to useful compounds in organic synthesis.

A novel method for the synthesis of 2‐chloro enesulfonamides via the one‐pot addition‐elimination of N‐chloro‐N‐fluorobenzenesulfonamides (CFBSA) to styrenes in the presence of Et3N is described. A total of 20 examples are presented to illustrate this concept including various of styrenes.