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Pd Catalysis in Cyanide-Free Synthesis of Nitriles from Haloarenes via Isoxazolines

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journal contribution
posted on 14.11.2016, 00:00 by Giovanni Maestri, Tatiana Cañeque, Nicola Della Ca’, Etienne Derat, Marta Catellani, Gian Paolo Chiusoli, Max Malacria
A method to obtain aryl nitriles from the corresponding halides by Pd catalysis, in the absence of any cyanide source, is reported. The reaction of an aryl halide, ethyl nitroacetate, and an olefin readily delivers an aromatic nitrile. A variety of aryl iodides/bromides have been converted into the corresponding cyanoarenes in fair to excellent yields. The reaction likely involves the following steps: (a) Pd-catalyzed α-arylation of ethyl nitroacetate; (b) nitrile oxide formation; (c) [3 + 2]-cycloaddition with an olefin to provide an isoxazoline; (d) isoxazoline cleavage to benzonitrile formation.

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