Palladium-Catalyzed Chelation-Assisted Aromatic C–H Nitration: Regiospecific Synthesis of Nitroarenes Free from the Effect of the Orientation Rules

Zhang, Wei; Lou, Shaojie; Liu, Yunkui; Xu, Zhenyuan

Palladium-Catalyzed Chelation-Assisted Aromatic C–H Nitration: Regiospecific Synthesis of Nitroarenes Free from the Effect of the Orientation Rules

2013

Zhang, Wei | Lou, Shaojie | Liu, Yunkui | Xu, Zhenyuan

A palladium-catalyzed chelation-assisted ortho-nitration of aryl C–H bond is described. A range of azaarenes such as 2-arylquinoxalines, pyridines, quinoline, and pyrazoles were nitrated with excellent chemo- and regioselectivity. Using the O-methyl oximyl group as a removable directing group, the regiospecific synthesis of a variety of o-nitro aryl ketones was achieved starting from aryl ketones via a three-step process involving the Pd-catalyzed ipso-nitration of C–H bond as a key step. Mechanistic investigations support a silver-mediated radical mechanism involving Pd((II/III) and/or Pd(II/IV) catalytic cycles under oxidizing conditions.

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