Abstract
A ruthenium‐grafted hydrotalcite (Ru/HT) and hydrotalcite‐supported palladium nanoparticles (Pd~nano~/HT) are easily prepared by treating basic layered double hydroxide, hydrotalcite (HT, Mg~6~Al~2~(OH)~16~CO~3~) with aqueous RuCl~3~⋅n H~2~O and K~2~[PdCl~4~] solutions, respectively, using surface impregnation methods. Analysis by means of X‐ray diffraction, and energy‐dispersive X‐ray, electron paramagnetic resonance, and X‐ray absorption fine structure spectroscopies proves that a monomeric Ru^IV^ species is grafted onto the surface of the HT. Meanwhile, after reduction of a surface‐isolated Pd^II^ species, highly dispersed Pd nanoclusters with a mean diameter of about 70 Å is observed on the Pd~nano~/HT surface by transmission electron microscopy analysis. These hydrotalcite‐supported metal catalysts can effectively promote α‐alkylation reactions of various nitriles with primary alcohols or carbonyl compounds through tandem reactions consisting of metal‐catalyzed oxidation and reduction, and an aldol reaction promoted by the base sites of the HT. In these catalytic α‐alkylations, homogeneous bases are unnecessary and the only by‐product is water. Additionally, these catalyst systems are applicable to one‐pot syntheses of glutaronitrile derivatives.