Nickel Catalyzed Cross-Coupling and Amination Reactions of Aryl Nitriles

 

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Abstract

Aryl nitriles have been found to participate in cross-coupling and amination reactions via nickel-catalyzed activation of the C-CN bond. With the development of these synthetically useful transformations, aryl nitriles can now be considered along with aryl halides and sulfonates as viable substrates for these types of reactions.

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This catalyst was prepared as described in the experimental section. Alternatively, it can be purchased from Aldrich (catalog number 56,767-1).

These results were obtained by GC analysis of a reaction sample (containing tridecane as an internal standard) quenched in a mixture of aq sodium citrate (1 M) and Et₂O.

A ‘spot test’ [9] confirmed the presence of cyanide ion in the aq phase of the quenched reaction mixture.

Among phosphines screened, the relative order of effectiveness in this biaryl cross coupling reaction is: Me₃P >> Me₂PPh = Et₃P > MePPh₂ = Me₂PCH₂CH₂PMe₂ > Ph₃P > (C₆H₁₁)₃P.