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A carbonylative cyclization of propargylic amines with elemental selenium to produce (E)‐5‐(iodomethylene)‐1,3‐selenazolidin‐2‐ones has been developed for the first time. Using DBU as the promoter and n‐C4F9I as the iodide source, various target compounds were produced up to 95 % yields. Notably, benzene‐1,3,5‐triyl triformate (TFBen) was employed as a safe and convenient solid CO source here.
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