Aminolysis of 4-Nitrobenzenesulfenyl Chloride

The reactions of 4-nitrobenzenesulfenyl chloride with substituted benzylamines proceed through three pathways, the uncatalyzed () and catalyzed () paths including solvolysis () by the solvent. The large value of primary normal kinetic isotope effects imply that the proton transfer occurs concurrently from benzylamine to Cl atom of the substrate. The and values for the catalyzed path, , are greater than those for the uncatalyzed path, indicating that greater degree of bond formation in the catalyzed TS compared to the uncatalyzed TS.