Monoalkylations with alcohols by a cascade reaction on bifunctional solid catalysts: Reaction kinetics and mechanism

A bifunctional catalytic system formed by Pd on MgO catalyzes the cascade process between benzyl alcohol and phenylacetonitrile, diethylmalonate and nitromethane, to give the respective α-monoalkylated products without external supply of hydrogen. The process involves a series of three cascade reactions occurring on different catalytic sites. The alcohol undergoes oxidation to the corresponding aldehyde with the simultaneous formation of a metal hydride; then, the aldehyde reacts with a nucleophile formed “in situ” to give an alkene, and finally, the hydrogen from the hydride is transferred to the alkene to give a new C–C bond.A kinetic study on the α-monoalkylation reaction of benzylacetonitrile with benzyl alcohol reveals that the rate-controlling step for the one-pot reaction sequence is the hydrogen transfer reaction from the surface hydrides to the olefin, and consequently, the global reaction rate is improved when decreasing the size of the Pd metal particle.

Graphical abstractPd-MgO catalyzes the α-monoalkylation of activated methylenic compounds with alcohols through a cascade process without external supply of hydrogen. A kinetic study shows that the rate controlling step for the one-pot sequence is the hydrogenation of the olefin by the surface metal hydrides.Figure optionsDownload full-size imageDownload high-quality image (69 K)Download as PowerPoint slideResearch highlights► Metal–based bifunctional solids catalyze monoalkylations reactions with alcohols. ► The sequential process is based on hydrogen transfer methodology. ► The rate-controlling step is the hydrogen transfer reaction from the surface hydrides to the olefin.