title: Chiral modification of platinum by co-adsorbed cinchonidine and trifluoroacetic acid: origin of enhanced stereocontrol in the hydrogenation of trifluoroacetophenone.
abstract: Cinchonidine (CD) adsorbed onto a platinum metal catalyst leads to rate acceleration and induces strong stereocontrol in the asymmetric hydrogenation of trifluoroacetophenone. Addition of catalytic amounts of trifluoroacetic acid (TFA) significantly enhances the enantiomeric excess from 50 to 92%. The origin of the enantioselectivity bestowed by co-adsorbed CD and TFA is investigated by using in situ attenuated total reflection infrared spectroscopy and modulation excitation spectroscopy. Molecular interactions between the chiral modifier (CD), acid additive (TFA) and the trifluoro-activated substrate at the solid-liquid interface are elucidated under conditions relevant to catalytic hydrogenations, that is, on a technical Pt/Al2O3 catalyst in the presence of H2 and solvent. Monitoring of the unmodified and modified surface during the hydrogenation provides an insight into the phenomenon of rate enhancement and the crucial interactions of CD with the ketone, corresponding product alcohol, and TFA. Comparison of the diastereomeric interactions occurring on the modified surface and in the liquid solution shows a striking difference for the chiral preferences of CD. The spectroscopic data, in combination with calculations of molecular structures and energies, sheds light on the reaction mechanism of the heterogeneous asymmetric hydrogenation of trifluoromethyl ketones and the involvement of TFA in the diastereomeric intermediate surface complex: the quinuclidine N atom of the adsorbed CD forms an N-H-O-type hydrogen-bonding interaction not only with the trifluoro-activated ketone but also with the corresponding alcohol and the acid additive. Strong evidence is provided that it is a monodentate acid/base adduct in which the carboxylate of TFA resides at the quinuclidine N-atom of CD, which imparts a better stereochemical control.
authors.affiliation: Department of Chemistry and Applied Biosciences, Institute for Chemical and Bioengineering, ETH Zürich, Hönggerberg, HCI, 8093 Zürich (Switzerland), Fax: (+41) 44-632-11-63.
authors.forename: Fabian
authors.initials: F
authors.lastname: Meemken
authors.forename: Alfons
authors.initials: A
authors.lastname: Baiker
authors.forename: Sebastian
authors.initials: S
authors.lastname: Schenker
authors.forename: Konrad
authors.initials: K
authors.lastname: Hungerbühler
mesh_terms: D000098:Acetophenones / Q000737:chemistry*; D000327:Adsorption; D000537:Aluminum Oxide / Q000737:chemistry; D002384:Catalysis; D002930:Cinchona Alkaloids / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D006860:Hydrogen Bonding; D006865:Hydrogenation; D007659:Ketones / Q000737:chemistry; D010984:Platinum / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D013055:Spectrophotometry, Infrared; D013237:Stereoisomerism; D014269:Trifluoroacetic Acid / Q000737:chemistry*
chemical_list: D000098:Acetophenones; D002930:Cinchona Alkaloids; D007659:Ketones; D012997:Solvents; C041622:cinchonidine; D010984:Platinum; D006859:Hydrogen; D014269:Trifluoroacetic Acid; D000537:Aluminum Oxide; C038699:acetophenone
keywords: IR spectroscopy; asymmetric catalysis; hydrogenation; ketones; platinum