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Density functional theory calculations and in situ characterizations demonstrate that the BiCu-SAA catalyst system promotes CO2 activation and subsequent C-C bond formation during the electrocatalytic reaction, thereby contributing to its notable C2+ selectivity. A method for palladium-catalyzed ring-opening [3 + 2]-annulation has been devised, applying it to spirovinylcyclopropanyl oxindoles and seven-membered cyclic N-sulfonyl