Synthesis and reactivity of isomeric Ru complexes with hydroxypyridyl fragment: Active catalysts for (3-alkylation of secondary alcohols with primary alcohols

When the ligand LOH, containing a 2-hydroxy pyridine group, reacts with an equimolar amount of the precursor Ru(DMSO)4Cl2, two isomeric ruthenium complexes are formed. These isomers are termed cis-1 and trans-1, based on the relative positions of the N atom in N-(2-(6-hydroxy pyridin-2-yl)phenyl)acetamide and the pyridine groups of bis((1,4-pyridin-2-yl)methyl)amine. Treatment of these isomers with equimolar amounts of NaH results in deprotonation of the uncoordinated hydroxy pyridine groups, leading to the formation of complex 2 with newly coordinated pyridine groups. The catalytic activity of these three ruthenium complexes in the (3-alkylation reaction of primary alcohols and secondary alcohols was evaluated, with complex 2 displaying the highest activity and selectivity. Complex 2 may be seen as an intermediate in the catalysis of the (3-alkylation reaction by the isomers (cis-1 and trans-1). These findings are valuable for the development of more effective bifunctional catalysts.