Unusual enantioselectivities in heterogeneous organocatalyzed reactions: Reversal of direction using proline di- versus tri-peptides in the aldol addition

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15 Citations (Scopus)

Abstract

The heterogeneous asymmetric direct aldol reactions between aldehydes (2-nitrobenzaldehyde, 2-methylpropanal) and ketones (acetone, cyclohexanone) in the presence of polystyrene (PS) resin supported di- and tripeptides were studied under otherwise identical experimental conditions at room temperature in batch reactor. For all three asymmetric aldol reactions reversal of enantiomeric excess was observed on H-Pro-Pro-Glu(OH)-PS catalyst (ee 39-50%) as compared to the H-Pro-Glu(OH)-PS catalyst (ee 52-95%). The determinant role of the conformation of the intermediate adducts held responsible for chiral induction is interpreted by quantum chemical calculations.

Original languageEnglish
Pages (from-to)86-92
Number of pages7
JournalJournal of Molecular Catalysis A: Chemical
Volume382
DOIs
Publication statusPublished - Feb 2014

Fingerprint

Enantioselectivity
Polystyrenes
Proline
Peptides
peptides
polystyrene
2-nitrobenzaldehyde
catalysts
Catalysts
Dipeptides
Batch reactors
Acetone
Ketones
Aldehydes
aldehydes
determinants
ketones
resins
acetone
adducts

Keywords

  • Aldol reaction
  • Asymmetric synthesis
  • Heterogeneous catalysis
  • Organocatalysis
  • Peptides

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry
  • Process Chemistry and Technology

Cite this

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title = "Unusual enantioselectivities in heterogeneous organocatalyzed reactions: Reversal of direction using proline di- versus tri-peptides in the aldol addition",
abstract = "The heterogeneous asymmetric direct aldol reactions between aldehydes (2-nitrobenzaldehyde, 2-methylpropanal) and ketones (acetone, cyclohexanone) in the presence of polystyrene (PS) resin supported di- and tripeptides were studied under otherwise identical experimental conditions at room temperature in batch reactor. For all three asymmetric aldol reactions reversal of enantiomeric excess was observed on H-Pro-Pro-Glu(OH)-PS catalyst (ee 39-50{\%}) as compared to the H-Pro-Glu(OH)-PS catalyst (ee 52-95{\%}). The determinant role of the conformation of the intermediate adducts held responsible for chiral induction is interpreted by quantum chemical calculations.",
keywords = "Aldol reaction, Asymmetric synthesis, Heterogeneous catalysis, Organocatalysis, Peptides",
author = "G. Sz{\"o}llősi and A. Cs{\'a}mpai and C. Somlai and M{\'o}nika Fekete and M. Bart{\'o}k",
year = "2014",
month = "2",
doi = "10.1016/j.molcata.2013.11.011",
language = "English",
volume = "382",
pages = "86--92",
journal = "Journal of Molecular Catalysis A: Chemical",
issn = "1381-1169",
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TY - JOUR

T1 - Unusual enantioselectivities in heterogeneous organocatalyzed reactions

T2 - Reversal of direction using proline di- versus tri-peptides in the aldol addition

AU - Szöllősi, G.

AU - Csámpai, A.

AU - Somlai, C.

AU - Fekete, Mónika

AU - Bartók, M.

PY - 2014/2

Y1 - 2014/2

N2 - The heterogeneous asymmetric direct aldol reactions between aldehydes (2-nitrobenzaldehyde, 2-methylpropanal) and ketones (acetone, cyclohexanone) in the presence of polystyrene (PS) resin supported di- and tripeptides were studied under otherwise identical experimental conditions at room temperature in batch reactor. For all three asymmetric aldol reactions reversal of enantiomeric excess was observed on H-Pro-Pro-Glu(OH)-PS catalyst (ee 39-50%) as compared to the H-Pro-Glu(OH)-PS catalyst (ee 52-95%). The determinant role of the conformation of the intermediate adducts held responsible for chiral induction is interpreted by quantum chemical calculations.

AB - The heterogeneous asymmetric direct aldol reactions between aldehydes (2-nitrobenzaldehyde, 2-methylpropanal) and ketones (acetone, cyclohexanone) in the presence of polystyrene (PS) resin supported di- and tripeptides were studied under otherwise identical experimental conditions at room temperature in batch reactor. For all three asymmetric aldol reactions reversal of enantiomeric excess was observed on H-Pro-Pro-Glu(OH)-PS catalyst (ee 39-50%) as compared to the H-Pro-Glu(OH)-PS catalyst (ee 52-95%). The determinant role of the conformation of the intermediate adducts held responsible for chiral induction is interpreted by quantum chemical calculations.

KW - Aldol reaction

KW - Asymmetric synthesis

KW - Heterogeneous catalysis

KW - Organocatalysis

KW - Peptides

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JO - Journal of Molecular Catalysis A: Chemical

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