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

Abstract

[EN] 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 alpha-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 alpha-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. (C) 2011 Elsevier Inc. All rights reserved.