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A simple and efficient method for the synthesis of dialdehyde aniline in good yields (up to 83%) is explored using Cu(OTf)2 as the catalyst, Selectfluor as the radical initiator, and DMSO as both the carbon and oxygen sources. Experimental studies indicate that the reaction is achieved by the formylation of two CAr-H bonds, first at the para-position and then at the ortho-position. A possible mechanism is proposed, including the thermal homolysis of Selectfluor, the Cu(II)-facilitated formylation of the CAr-H bonds, and the hydrolysis of the amide under alkaline conditions in air atmosphere.

A simple and efficient method is explored for the synthesis of 2-hydroxyimino-2-phenylacetonitriles (2) and phthalimides (4), by using nitromethane as nitrogen donors. Both reactions are promoted by Cu(II) system with the participation of dioxygen as an oxidant. The scope of the method has been successfully demonstrated with a total of 51 examples. The flexible and diversified characteristics of reactions are introduced in terms of electronic effect, steric effect, position of substituted groups, and intramolecular charge transfer. Experimental studies suggest that the methyl nitrite could be a precursor in the path to the final products. A possible reaction mechanism is proposed, including the Cu(II)/O2-facilitated transformation of nitromethane to methyl nitrite, the base-induced formation of 2-hydroxyimino-2-phenylacetonitriles, and the base-dioxygen-promoted formation of phthalimides.