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Synthesis 2003(11): 1643-1648
DOI: 10.1055/s-2003-40873
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Nickel Catalyzed Cross-Coupling and Amination Reactions of Aryl Nitriles

Joseph A. Miller*, John W. Dankwardt, Jonathan M. Penney
DSM Pharmaceuticals, Inc, 5900 NW Greenville Blvd., Greenville, NC 27834, USA
e-Mail: joe.miller@dsm.com;
Further Information

Publication History

Received 29 April 2003
Publication Date:
25 July 2003 (online)

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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.

Key words

nitriles - nickel - cross-coupling - biaryls - aminations

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6

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

7

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.

8

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

10

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