Origin of proposed mechanistic models in heterogeneous catalytic enantioselective hydrogenation of pyruvates comes from the conformation properties of internal rotation of cinchona alkaloids

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Abstract

The main orientations of methyl pyruvate in the force field of cinchonia alkaloids have been fully mapped and analyzed using molecular mechanics building techniques and density functional theory methods. Beside the known "open (3), (4)" and "closed (1), (2)" forms of cinchonidine, its group of "open (10), (11)" conformation is also analyzed, as well as the potential surface of isocinchonines. In this way an origin of different mechanistic models by different authors for the hydrogenation of activated ketones on cinchona alkaloid modified platinum is revealed: All models can be originated from the conformational properties of the internal rotation of the two-ring system in cinchona alkaloids (particularly cinchonidine, α and β-isocinchonine) with and without methyl pyruvate adduct formation.

Original languageEnglish
Pages (from-to)21700-21712
Number of pages13
JournalJournal of Physical Chemistry C
Volume113
Issue number52
DOIs
Publication statusPublished - 2009

Fingerprint

Pyruvates
Cinchona Alkaloids
pyruvates
alkaloids
Hydrogenation
hydrogenation
Conformations
Alkaloids
Molecular mechanics
Surface potential
Platinum
Ketones
Density functional theory
ketones
field theory (physics)
adducts
platinum
density functional theory
rings
methyl pyruvate

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

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title = "Origin of proposed mechanistic models in heterogeneous catalytic enantioselective hydrogenation of pyruvates comes from the conformation properties of internal rotation of cinchona alkaloids",
abstract = "The main orientations of methyl pyruvate in the force field of cinchonia alkaloids have been fully mapped and analyzed using molecular mechanics building techniques and density functional theory methods. Beside the known {"}open (3), (4){"} and {"}closed (1), (2){"} forms of cinchonidine, its group of {"}open (10), (11){"} conformation is also analyzed, as well as the potential surface of isocinchonines. In this way an origin of different mechanistic models by different authors for the hydrogenation of activated ketones on cinchona alkaloid modified platinum is revealed: All models can be originated from the conformational properties of the internal rotation of the two-ring system in cinchona alkaloids (particularly cinchonidine, α and β-isocinchonine) with and without methyl pyruvate adduct formation.",
author = "S. Kristy{\'a}n",
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pages = "21700--21712",
journal = "Journal of Physical Chemistry C",
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publisher = "American Chemical Society",
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AU - Kristyán, S.

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AB - The main orientations of methyl pyruvate in the force field of cinchonia alkaloids have been fully mapped and analyzed using molecular mechanics building techniques and density functional theory methods. Beside the known "open (3), (4)" and "closed (1), (2)" forms of cinchonidine, its group of "open (10), (11)" conformation is also analyzed, as well as the potential surface of isocinchonines. In this way an origin of different mechanistic models by different authors for the hydrogenation of activated ketones on cinchona alkaloid modified platinum is revealed: All models can be originated from the conformational properties of the internal rotation of the two-ring system in cinchona alkaloids (particularly cinchonidine, α and β-isocinchonine) with and without methyl pyruvate adduct formation.

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