We report a practical and environmentally benign method for the oxidative Ritter‐type chloroamidation of alkenes using sodium chloride and oxone as a chlorinating source and an oxidant, respectively, in acetonitrile under mild conditions. The reaction proceeded smoothly under non‐aqueous conditions without the use of any catalyst. Excellent chemoselectivity (i. e., chloroamidation versus dichlorination) could be achieved for electron‐deficient styrenes. In addition, this protocol could be easily applied to 7‐gram‐scale synthesis.
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