Joseph A. Miller
Tetrahedron Letters; 2001, 42, 6991–6993
DOI:10.1016/S0040-4039(01)01476-9
Summary: Nickel catalysts have been known to coordinate and subsequently activate the C-CN bond of nitrile compounds. However, a practical procedure to perform a cross-coupling reaction with these substrates and an appropriate organometallic was unknown until the present work. Thus, reaction of a benzonitrile with an aryl Grignard derivative in the presence of a Ni catalyst, such as [NiCl2(PMe3)2], provides the corresponding unsymmetrical biaryl in high yield and with high selectivity. Ligand screening found that trimethylphosphine was the most effective ligand. The Grignard reagent was modified (for example, ArMgOt-Bu) to reduce the amount of direct addition of the organomagnesium reagent to the nitrile. This group has also expanded the methodology to alkyl, alkenyl, and alkynyl organometallics.
16 examples, 69-97% yield
