Ruthenium-Catalyzed Regioselective 1,4-Hydroboration of Pyridines.

Simple ruthenium precursor [Ru(p-cymene)Cl2]2 1 catalyzed regioselective 1,4-dearomatization of pyridine derivatives using pinacolborane is reported. Two catalytic intermediates, [Ru(p-cymene)Cl2Py] 2 and [Ru(p-cymene)Cl2(P(Cy)3)] 3, involved in this process are identified, independently synthesized, characterized, and further used directly as effective catalysts; two more catalytic intermediates [Ru(p-cymene)Cl2(Py)(P(Cy)3)] 4 and [Ru(p-cymene)(H)Cl(Py)(P(Cy)3)] 5 are identified in solution. Complex 5 is the active catalytic intermediate. An intramolecular selective 1,5-hydride transfer in 5 leading to the regioselective 1,4-hydroboration of pyridine compounds is proposed.