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One‐pot (CF3CO)2O/K2CO3‐mediated tandem cyclocondensation of β‐ketosulfones with carboxylic acids provides diversified 3‐sulfonylchromones in good to excellent yields by refluxing MeCN under high‐pressure (using a sealed tube) and dry‐nitrogen atmospheric conditions. This study proposed and discussed a plausible mechanism. The paper also described the formation of 3‐sulfonylflavones and gram‐scale...