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An operationally simple and efficient cascade approach to access a series of 1,3‐thiazinanes has been developed through intermolecular [3+3] heteroannulative coupling employing β‐ketothioamide as a C1 N1S1 unit and epichlorohydrin as a C3 unit at room temperature for the first time. The reaction proceeds by nucleophilic attack of thiocarbonyl sulfur to less hindered primary carbon of oxirane followed...