Influence of adsorption geometry in the heterogeneous enantioselective catalytic hydrogenation of a prototypical enone

Beaumont, S., Kyriakou, G., Watson, D. J., Vaughan, O., Papageorgiou, A. and Lambert, R. (2010) Influence of adsorption geometry in the heterogeneous enantioselective catalytic hydrogenation of a prototypical enone. Journal of Physical Chemistry C, 114 (35). pp. 15075-15077. ISSN 1932-7447 doi: 10.1021/jp105960w

Abstract/Summary

Asymmetric catalysis is of paramount importance in organic synthesis and, in current practice, is achieved by means of homogeneous catalysts. The ability to catalyze such reactions heterogeneously would have a major impact both in the research laboratory and in the production of fine chemicals and pharmaceuticals, yet heterogeneous asymmetric hydrogenation of C═C bonds remains hardly explored. Very recently, we demonstrated how chiral ligands that anchor robustly to the surface of Pd nanoparticles promote asymmetric catalytic hydrogenation: ligand rigidity and stereochemistry emerged as key factors. Here, we address a complementary question: how does the enone reactant adsorb on the metal surface, and what implications does this have for the enantiodifferentiating interaction with the surface-tethered chiral modifiers? A reaction model is proposed, which correctly predicts the identity of the enantiomer experimentally observed in excess.