February 2008   (Technical report   )

Activation in Prochiral Reaction Assemblies on Pt(111)

Marc-Andre Laliberte, Stephane Lavoie, Bjørk Hammer, Gautier Mahieu, Peter McBreen

Trifluoroacetophenone (TFAP) forms C=O···H-C bonded dimers and trimers at room temperature on Pt(111). It is proposed that these systems mimic the prochiral carbonyl chiral modifier interaction in the enantioselective hydrogenation of TFAP on cinchona-modified Pt catalysts. That is, the activation of TFAP in homomolecular assemblies at racemic sites is expected to be roughly the same as in the diastereomeric complex formed at chiral sites. This interpretation suggests a reason why alpha-phenyl ketones do not display a strong measured rate enhancement effect in the Orito reaction.

http://pubs.acs.org/doi/abs/10.1021/ja710297b