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Scientific article
English

Conformational rigidity: a necessary prerequisite of chiral modifiers used in heterogeneous enantioselective catalysis?

Published inJournal of catalysis, vol. 232, no. 1, p. 137-142
Publication date2005
Abstract

In the hydrogenation of ketopantolactone, the (R,R) and (R,S) diastereomers of a new chiral modifier, pantoyl-naphthylethylamine, afforded 74 and 40% ee, respectively, to (R)-pantolactone. On the basis of NOE studies and theoretical calculations, the different properties of the diastereomers and in particular the effect of acid on the modifier structure are deduced from differences in conformational rigidity and steric constraint. In case of the (R,R)-diastereomer, a loose, extended structure in apolar solvent changes to a compact conformation via an additional intramolecular hydrogen bond, resulting in a more defined "chiral pocket" available for the reactant on the Pt surface.

Keywords
  • Acid effect
  • Asymmetric heterogeneous catalysis
  • Pt/Al2O3
  • Ketopantolactone
  • Hydrogenation
  • Ab initio calculation
  • NOE
  • Modifier conformation
Citation (ISO format)
ORGLMEISTER, Elisabeth et al. Conformational rigidity: a necessary prerequisite of chiral modifiers used in heterogeneous enantioselective catalysis? In: Journal of catalysis, 2005, vol. 232, n° 1, p. 137–142. doi: 10.1016/j.jcat.2005.03.005
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ISSN of the journal0021-9517
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