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A novel one‐pot two‐step multicomponent reaction has been achieved for the preparation of β‐CF3 enamines by using different aliphatic amines, propiolates, and CF3SO2Na as starting material. In this protocol, various aliphatic amines including primary amines, cyclic or acyclic secondary amines were demonstrated to be good coupling partners, and different β‐CF3 enamines were obtained in moderate to...