Abstract
Metal-mediated reactions between cis-[PdCl2(CNR)2] (R = Xy (1), Cy (2), tBu (3), C6H3(Cl-2)Me-6 (4)) and the ketonitrones Ph2C═N(O)C6H4R′ (R′ = Me (5), Cl (6)) proceed in a 1:1 molar ratio as selective nucleophilic oxygenations and provide the imine–isocyanide complexes [PdCl2{N(C6H4R′)═CPh2}(CNR)] (7–14: R′ = Me, R = Xy (7), Cy (8), tBu (9), C6H3(Cl-2)Me-6 (10); R′ = Cl, R = Xy (11), Cy (12), tBu (13), C6H3(Cl-2)Me-6 (14)) in excellent yields (90–94%), while the reaction of the cis-[PdCl2(CNR)2] complexes with aldonitrones proceeds as 1,3-dipolar cycloaddition, giving carbene adducts which then convert to the imine complexes. Theoretical calculations at the DFT level indicate that, in the case of aldonitrones, formation of the imine complexes occurs preferably via a cycloaddition/splitting pathway, including the generation of a cycloadduct, while, in the case of ketonitrones, both the cycloaddition/splitting route and the direct oxygen atom transfer pathway are equally plausible from a kinetic viewpoint....
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