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The reaction of N‐arylpropynamides with the commercially available trifluoromethanesulfanamide in the presence of BiCl3 was found to afford quinolin‐2‐ones in a selective manner via electrophilic trifluoromethylthiolation enabled by the in‐situ generated CF3S−Cl and the followed intramolecular cyclization. Differing from the existing analogous cyclization route that solely produces spiro[4,5]trienones,...