Catalyst‐free Chloroamination Cyclization Cascade with Sodium Hypochlorite: from N‐(Pentenyl)sulfonylamides to 2‐(1‐Chloromethyl)pyrrolidines

A mild and catalyst-free protocol to obtain several 2-chloromethylpyrrolidines by the use of a commercial solution of sodium hypochlorite is here reported, without the need for a light source. The choice of the solvent revealed to be crucial in the success of the reaction. Mechanistic studies, both experimental and computational, confirmed a radical mechanism, where the deprotonation step, followed by the oxidation of a N-centered anion to the corresponding radical, allowed 2-chloromethylpyrrolidines, by a very fast cyclization, to be obtained. Sodium hypochlorite plays the role of both the oxidant and the chlorine source.