The reaction of 2-phenylpyridines with anilines in the presence of Cu(OAc)2 as a promoter results in selective mono-amination of the ortho C–H bonds in 2-phenylpyridines to give amine derivatives in high yields per the conversion. This is the rare example of the functionalization of C–H bonds to C–N bonds.

To demonstrate the utility of isocyanides in catalytic C−H bond functionalization reactions, a palladium-catalyzed cyclocoupling reaction of 2-halobiaryls with isocyanides was developed. The reaction afforded an array of fluorenone imine derivatives via the cleavage of a C−H bond at the 2′-position of 2-halobiaryls. The use of 2,6-disubstituted phenyl isocyanide was crucial for this catalytic cyclocoupling reaction to proceed. The reaction was applicable to heterocyclic and vinylic substrates, allowing the construction of a wide range of ring system. The large kinetic isotope effect observed (k H/k D = 5.3) indicates that C−H bond activation was the turnover-limiting step in this catalysis.

Other Cu salts such as CuCl, CuI, Cu(OTf), CuBr2, CuO or Cu(O-CO-CF3)2 as promoter of the amination reaction are less useful. -(UEMURA, T.; IMOTO, S.; CHATANI*, N.; Chem. Lett. 35 (2006) 8, 842-843;

Ru/C also exhibits catalytic activity for carbonylation at ortho-C-H bonds in 2-phenylpyridines.

Pyridine derivatives R 0380Ru/C-Catalyzed Carbonylation at ortho-C-H Bonds in 2-Phenylpyridines. -The reaction of substituted 2-phenylpyridines, -pyrimidine, -oxazole and -pyrazole affords generally the monocarbonylation products. The reaction is also applicable to the carbonylation of naphthalene derivative (XIII) and 2-(2-thienyl)pyridine (XV). -(IMOTO, S.; UEMURA, T.; KAKIUCHI, F.; CHATANI*, N.; Synlett 2007, 1, 170-172; Dep. Appl. Chem., Fac. Eng., Osaka Univ., Suita, Osaka 565, Japan; Eng.) -R. Steudel 19-139