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A practical and efficient method for the synthesis of α-fluorothioacrylamide was developed from selective defluorinative sulfuration of trifluoropropanamides with disulfides. The N-chelation-assisted copper-catalyzed defluorination and sulfurization reactions feature excellent functional group tolerance and incorporation of both sulfur atoms of disulfides into acrylamides.Pyrrolizidine alkaloids (PAs) are found to be toxic pollutants emitted into the environment by numerous plant species, resulting in contamination. In this article, w