Quantitative Expression of Dynamic Kinetic Resolution of Chirally Labile Enantiomers: Stereoselective Hydrogenation of 2-Substituted 3-Oxo Carboxylic Esters Catalyzed by BINAP-Ruthenium(II) Complexes

M. Kitamura, Makoto Tokunaga, R. Noyori

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165 Citations (Scopus)

Abstract

Hydrogenation of chirally unstable 2-substituted 3-oxo carboxylic esters gives a mixture of four stereoisomeric hydroxy esters. Use of BINAP-Ru(II) complex catalysts allows selective production of one stereoisomer among four possible isomers. The stereoselectivity obtained by the dynamic kinetic resolution depends on facile in situ racemization of the substrates, efficient chirality recognition ability of the catalysts, and the structures of the ketonic substrate. The factors controlling the efficiency of the stereoselective hydrogenation are experimentally determined by reaction of racemic oxo esters using enantiomerically pure and racemic BINAP complexes. Quantitative expression of the dynamic kinetic resolution has been made by defining the product partition coefficients (w, x, y, and z), the relative reactivities of the enantiomeric substrates (kfast/kSl0W), and the relative ease with which stereoinversion and hydrogenation take place (kinv/kfast). The validity of the equations has been demonstrated by the graphical exhibition of the enantioselectivity and diastereoselectivity as a function of conversion of the substrates.

Original languageEnglish
Pages (from-to)144-152
Number of pages9
JournalJournal of the American Chemical Society
Volume115
Issue number1
DOIs
Publication statusPublished - Jan 1 1993

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Hydrogenation
Ruthenium
Enantiomers
Esters
Kinetics
Substrates
Stereoisomerism
Stereoselectivity
Catalysts
Chirality
Enantioselectivity
Isomers
2-naphthol BINAP

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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title = "Quantitative Expression of Dynamic Kinetic Resolution of Chirally Labile Enantiomers: Stereoselective Hydrogenation of 2-Substituted 3-Oxo Carboxylic Esters Catalyzed by BINAP-Ruthenium(II) Complexes",
abstract = "Hydrogenation of chirally unstable 2-substituted 3-oxo carboxylic esters gives a mixture of four stereoisomeric hydroxy esters. Use of BINAP-Ru(II) complex catalysts allows selective production of one stereoisomer among four possible isomers. The stereoselectivity obtained by the dynamic kinetic resolution depends on facile in situ racemization of the substrates, efficient chirality recognition ability of the catalysts, and the structures of the ketonic substrate. The factors controlling the efficiency of the stereoselective hydrogenation are experimentally determined by reaction of racemic oxo esters using enantiomerically pure and racemic BINAP complexes. Quantitative expression of the dynamic kinetic resolution has been made by defining the product partition coefficients (w, x, y, and z), the relative reactivities of the enantiomeric substrates (kfast/kSl0W), and the relative ease with which stereoinversion and hydrogenation take place (kinv/kfast). The validity of the equations has been demonstrated by the graphical exhibition of the enantioselectivity and diastereoselectivity as a function of conversion of the substrates.",
author = "M. Kitamura and Makoto Tokunaga and R. Noyori",
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N2 - Hydrogenation of chirally unstable 2-substituted 3-oxo carboxylic esters gives a mixture of four stereoisomeric hydroxy esters. Use of BINAP-Ru(II) complex catalysts allows selective production of one stereoisomer among four possible isomers. The stereoselectivity obtained by the dynamic kinetic resolution depends on facile in situ racemization of the substrates, efficient chirality recognition ability of the catalysts, and the structures of the ketonic substrate. The factors controlling the efficiency of the stereoselective hydrogenation are experimentally determined by reaction of racemic oxo esters using enantiomerically pure and racemic BINAP complexes. Quantitative expression of the dynamic kinetic resolution has been made by defining the product partition coefficients (w, x, y, and z), the relative reactivities of the enantiomeric substrates (kfast/kSl0W), and the relative ease with which stereoinversion and hydrogenation take place (kinv/kfast). The validity of the equations has been demonstrated by the graphical exhibition of the enantioselectivity and diastereoselectivity as a function of conversion of the substrates.

AB - Hydrogenation of chirally unstable 2-substituted 3-oxo carboxylic esters gives a mixture of four stereoisomeric hydroxy esters. Use of BINAP-Ru(II) complex catalysts allows selective production of one stereoisomer among four possible isomers. The stereoselectivity obtained by the dynamic kinetic resolution depends on facile in situ racemization of the substrates, efficient chirality recognition ability of the catalysts, and the structures of the ketonic substrate. The factors controlling the efficiency of the stereoselective hydrogenation are experimentally determined by reaction of racemic oxo esters using enantiomerically pure and racemic BINAP complexes. Quantitative expression of the dynamic kinetic resolution has been made by defining the product partition coefficients (w, x, y, and z), the relative reactivities of the enantiomeric substrates (kfast/kSl0W), and the relative ease with which stereoinversion and hydrogenation take place (kinv/kfast). The validity of the equations has been demonstrated by the graphical exhibition of the enantioselectivity and diastereoselectivity as a function of conversion of the substrates.

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