Fundamental Investigations of Enantioselective Heterogeneous Catalysis

Abstract

Enantioselective catalysis is an increasingly important method of providing enantiomeric compounds for the pharmaceutical and agrochemical industries. To date, heterogeneous catalysts have failed to match the industrial impact achieved by homogeneous systems. One successful approach to the creation of heterogeneous enantioselective catalysts has involved the modification of conventional metal particle catalysts by the adsorption of chiral molecules. This article examines the contribution of effects such as chiral recognition and amplification to these types of system and how insight provided by surface science model studies may be exploited in the design of more effective catalysts.

Controlled metal nanostructures: Fertile ground for coordination chemists

“…One successful approach has involved the modification of conventional NPs by the adsorption of chiral molecules [269]. The most known catalytic reactions are the hydrogenation of activated C=C bonds [270] (mainly Pd catalysts modified with cinchona alkaloids), -ketoesters [271], [272], (mainly Pt catalysts modified with cinchona alkaloids and related modifiers) and -ketoesters [273] (mainly Raney Ni systems modified with tartaric acid).…”

Adsorption of Methyl Acetoacetate at Ni{111}: Experiment and Theory

“…This progress has been driven by the growing demand for optically pure chemicals in drug manufacturing, as well as by the refinement of experimental surface characterization techniques and theoretical methods of modelling adsorption and surface reactions. [3][4][5][6] Heterogeneous catalysts avoid the problem of phase separation that is inherent in homogeneous catalytic processes, which are predominantly used today. 7 Therefore, viable heterogeneous routes for enantio-pure building blocks of pharmaceuticals and other fine chemicals would make their production significantly greener and more economical.…”

Heterogeneous Enantioselective Hydrogenation in a Continuous-flow Fixed-bed Reactor System: Hydrogenation of Activated Ketones and Their Binary Mixtures on Pt–Alumina–Cinchona Alkaloid Catalysts

“…Some of the conversion data (C Si ) in Table 1 indicate inconsistent reproducibility: it is well-known that catalyst systems treated with chiral modifiers are somewhat more sensitive than unmodified hydrogenation catalysts. The reason for this is, among others, that depending on the initial state of the catalyst, the chiral modifier brings about dynamic and continuous changes in the structure of the active sites [28,[33][34][35][36][37][38][39][40]. This effect of the modifier also depends on its irreversible adsorption under the different conditions of the reactions [34,41,42].…”