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The Au(I)‐catalyzed reactions of (2‐alkynyl)phenylsulfonyl azetidines bearing terminal and non‐terminal alkynes in the presence of methanol as protic nucleophile to form benzosultams derivatives were studied by density functional theory (DFT) calculations. Our study highlights that gold(I) catalyzed nucleophilic addition of the nitrogen on the alkyne is favored over the direct ring opening of the...