Journal of Organic Chemistry 2007-07-06

Nickel-NHC-catalyzed alpha-arylation of acyclic ketones and amination of haloarenes and unexpected preferential N-arylation of 4-aminopropiophenone.

Kouki Matsubara, Keita Ueno, Yuji Koga, Kenji Hara

Index: J. Org. Chem. 72 , 5069, (2007)

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Abstract

Arylation of both acyclic ketones and primary and secondary amines was achieved using a new, simple, stable, and easy-to-access nickel(II)-halide complex bearing mixed PPh3/N-heterocyclic carbene ligands as a catalyst precursor. Acyclic ketones were first arylated at the alpha-position with the nickel catalyst. On the other hand, less basic amines, such as diphenylamine and 4-aminobenzophenone, were more favorable in the catalytic amination of haloarenes than basic amines, contrary to previous reports. N-Arylation of 4-aminopropiophenone was found to proceed selectively without causing alpha-arylation of the ketone group.