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Scientific article
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Adsorption of cinchonidine on platinum: a DFT insight in the mechanism of enantioselective hydrogenation of activated ketones

Published inJournal of catalysis, vol. 226, no. 1, p. 69-82
Publication date2004
Abstract

The adsorption of cinchonidine on platinum has been calculated with relativistically corrected density-functional theory, by first studying the interaction of the 1(S)-(4-quinolinyl)ethanol with a platinum cluster of 31 metal atoms, and by successive addition and separate optimization of the quinuclidine moiety. The conformations of the alkaloid on the surface were analyzed and their possible interactions with a surface chemisorbed methylpyruvate and acetophenone are discussed. A chiral space that is able to selectively accommodate surface enantiomers and to promote their rapid hydrogenation in a ligand-accelerated fashion has been determined. The role of the O-alkylation of the alkaloid in the modulation of enantioselectivity has been rationalized within the new interaction model.

Keywords
  • Cinchonidine
  • Adsorption
  • DFT
  • Platinum
  • Enantioselective hydrogenation
  • Activated ketones
  • Mechanism
Citation (ISO format)
VARGAS, Angelo, BUERGI, Thomas, BAIKER, Alfons. Adsorption of cinchonidine on platinum: a DFT insight in the mechanism of enantioselective hydrogenation of activated ketones. In: Journal of catalysis, 2004, vol. 226, n° 1, p. 69–82. doi: 10.1016/j.jcat.2004.05.011
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ISSN of the journal0021-9517
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