The origin of chemo- and enantioselectivity in the hydrogenation of diketones on platinum.
In the Pt-catalyzed hydrogenation of 1,1,1-trifluoro-2,4-diketones, addition of trace amounts of cinchonidine, O-methyl-cinchonidine, or (R,R)-pantoyl-naphthylethylamine induces up to 93% ee and enhances the chemoselectivity up to 100% in the hydrogenation of the activated carbonyl group to an OH function. A combined catalytic, NMR and FTIR spectroscopic, and theoretical study revealed that the two phenomena are coupled, offering the unique possibility for understanding the substrate-modifier-metal interactions. The high chemo- and enantioselectivities are attributed to the formation of an ion pair involving the protonated amine function of the chiral modifier and the enolate form of the substrate. DFT calculations including the simulation of the interaction of a protonated amine with the enolate adsorbed on a Pt 31 cluster revealed that only the C-O bond next to the CF3 group of the substrate is in direct contact with Pt and can be hydrogenated. The present study illustrates the fundamental role played by the metal surface and indicates that also the enol form can be the reactive species in the hydrogenation of the activated ketone on chirally modified Pt.
Department of Chemistry and Applied Biosciences, ETH Zurich, Hönggerberg, HCI, CH-8093 Zurich, Switzerland.
Simon
S
Diezi
Davide
D
Ferri
Angelo
A
Vargas
Tamas
T
Mallat
Alfons
A
Baiker
D000438:Alcohols / Q000138:chemical synthesis*; D002384:Catalysis; D002930:Cinchona Alkaloids / Q000737:chemistry; D005021:Ethylamines / Q000737:chemistry; D006865:Hydrogenation; D007659:Ketones / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D009281:Naphthalenes / Q000737:chemistry; D010984:Platinum / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared; D013237:Stereoisomerism
D000438:Alcohols; D002930:Cinchona Alkaloids; D005021:Ethylamines; D007659:Ketones; D009281:Naphthalenes; C041622:cinchonidine; D010984:Platinum