Triorganoindium Reagents in Rh-Catalyzed C⁻H Activation/C⁻C Cross-Coupling Reactions of 2-Arylpyridines.

The activation of C⁻H bonds through catalytic reactions using transition metals is an important challenge in organic chemistry in which the intermediates are related to those produced in the classical cross-coupling reactions. As part of our research program devoted to the development of metal-catalyzed reactions using indium organometallics, a protocol for the C⁻H activation and C⁻C coupling of 2-arylpyridines with triorganoindium reagents under Rh(I) catalysis is reported. Under the optimized conditions, we found that Me₃In and Ar₃In reagents reacted with 2-arylpyridines and related compounds in the presence of Rh(PPh₃)₃Cl, in PhCl/THF (9:1), at 120 °C for 48 h, to afford the ortho-coupling products in moderate to good yields. The nitrogen atom in the pyridine ring acts as a directing group to assist the functionalization at the ortho position of the aryl group forming a new C⁻C bond at this position.