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The gold‐catalyzed regioselective formation of 3‐hydroxyquinoline is accessed by combining anthranils and alkynyl sulfones. The selective scission of the epoxide intermediate stems from the thermodynamic stability difference of the resultant cation according to quantum chemical calculations. The subsequent semi‐pinacol rearrangement leads to the 1,2‐shift of an aryl or alkyl group originating from...