November 2011   (Technical report   )

Direct Observation of Molecular Preorganization for Chirality Transfer on a Catalyst Surface. Science 2011, 334, 776

Vincent Demers-Carpentier, Guillaume Goubert, Federico Masini, Raphael Lafleur-Lambert, Yi Dong, Stephane Lavoie, Gautier Mahieu, John Boukouvalas, Haili Gao, Anton Rasmussen, Lara Ferrighi, Yunxiang Pan, Bjørk Hammer, Peter McBreen

The chemisorption of specific optically active compounds on metal surfaces can create catalytically active chirality transfer sites. However, the mechanism through which these sites bias the stereoselectivity of reactions (typically hydrogenations) is generally assumed to be so complex that continued progress in the area is uncertain. We show that the investigation of heterogeneous asymmetric induction with single-site resolution sufficient to distinguish stereochemical conformations at the submolecular level is finally accessible. A combination of scanning tunneling microscopy and density functional theory calculations reveals the stereodirecting forces governing preorganization into precise chiral modifier-substrate bimolecular surface complexes. The study shows that the chiral modifier induces prochiral switching on the surface and that different prochiral ratios prevail at different submolecular binding sites on the modifier at the reaction temperature.

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www.sciencemag.org/content/334/6057/776.abstract