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A novel chlorolactamization reaction of homoallylic amines has been developed. The treatment of homoallylic amines with dimethylzinc in chloroform led to the formation of the corresponding β‐chlorolactams via the Prins‐type cyclization of a carbamoyl chloride intermediate. The results of this study highlight the synthetic utility of chloroform as a source of both carbonyl group and chloride anion.
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