Chiral sulfonated phosphines. Rhodium(I)-catalyzed asymmetric hydrogenolysis of epoxides

J. Bakos, Árpád Orosz, Stefánia Cserépi, Imre Tóth, Denis Sinou

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

Rhodium(I) complexes of sulfonated (-)-(2S,4S)-2,4-bis(diphenylphosphino)pentane ((S,S)-(BDPP)) are effective as catalyst for asymmetric hydrogenolysis of sodium cis-epoxysuccinate to sodium hydroxysuccinate in aqueous-organic two phase solvent system or in aqueous solution. It has been shown by deuterium labelling studies that both hydrogen and water participate in the aqueous hydrogenolysis as reactants and the reaction proceeds via the direct C-O bond cleavage of the epoxy group. High pressure NMR studies show the presence of rhodaoxetane-BDPP complexes as catalytic intermediates, which are formed by the oxidative addition of the epoxide to unsaturated Rh(I) species. Accordingly, a reaction mechanism has been proposed for the aqueous catalytic process. The use of a racemic substrate, sodium trans-phenylglycidate with the aqueous Rh-sulfonated (S,S)-BDPP system results in the kinetic resolution of the (2S,3R)-epoxide enantiomer. Thus, asymmetric aqueous catalytic hydrogenolysis could be a useful synthetic approach not only to chiral α-hydroxycarboxylic acid derivatives but also to chiral trans-substituted epoxides.

Original languageEnglish
Pages (from-to)85-97
Number of pages13
JournalJournal of Molecular Catalysis A: Chemical
Volume116
Issue number1-2
DOIs
Publication statusPublished - Feb 24 1997

Fingerprint

Phosphines
hydrogenolysis
Hydrogenolysis
Rhodium
epoxy compounds
Epoxy Compounds
rhodium
phosphines
Sodium
sodium
Enantiomers
Deuterium
pentanes
enantiomers
Labeling
marking
deuterium
cleavage
Hydrogen
Nuclear magnetic resonance

Keywords

  • Asymmetric hydrogenolysis
  • Epoxides
  • Rhodium complexes
  • Sulfonated (S,S)-BDPP complexes

ASJC Scopus subject areas

  • Catalysis
  • Process Chemistry and Technology

Cite this

Chiral sulfonated phosphines. Rhodium(I)-catalyzed asymmetric hydrogenolysis of epoxides. / Bakos, J.; Orosz, Árpád; Cserépi, Stefánia; Tóth, Imre; Sinou, Denis.

In: Journal of Molecular Catalysis A: Chemical, Vol. 116, No. 1-2, 24.02.1997, p. 85-97.

Research output: Contribution to journalArticle

Bakos, J. ; Orosz, Árpád ; Cserépi, Stefánia ; Tóth, Imre ; Sinou, Denis. / Chiral sulfonated phosphines. Rhodium(I)-catalyzed asymmetric hydrogenolysis of epoxides. In: Journal of Molecular Catalysis A: Chemical. 1997 ; Vol. 116, No. 1-2. pp. 85-97.
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