Influence of Adsorption Geometry in the Heterogeneous Enantioselective Catalytic Hydrogenation of a Prototypical Enone

Beaumont, Simon K.; Kyriakou, Georgios; Watson, David J.; Vaughan, Owain P.H.; Papageorgiou, Anthoula C.; Lambert, Richard M.

Abstract

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.

Citation

Beaumont, S. K., Kyriakou, G., Watson, D. J., Vaughan, O. P., Papageorgiou, A. C., & Lambert, R. M. (2010). Influence of Adsorption Geometry in the Heterogeneous Enantioselective Catalytic Hydrogenation of a Prototypical Enone. Journal of Physical Chemistry C, 114(35), 15075-15077. https://doi.org/10.1021/jp105960w

• Journal Article Type: Article
• Publication Date: Aug 18, 2010
• Deposit Date: Mar 8, 2014
• Publicly Available Date: Apr 15, 2014
• Journal: Journal of Physical Chemistry C
• Print ISSN: 1932-7447
• Electronic ISSN: 1932-7455
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 114
• Issue: 35
• Pages: 15075-15077
• DOI: https://doi.org/10.1021/jp105960w
• Public URL: https://durham-repository.worktribe.com/output/1437323