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Asymmetric Anion-π Catalysis: Enamine Addition to Nitroolefins on π-Acidic Surfaces.
Journal article

Asymmetric Anion-π Catalysis: Enamine Addition to Nitroolefins on π-Acidic Surfaces.

  • Zhao Y Department of Organic Chemistry, University of Geneva , Geneva CH-1211, Switzerland.
  • Cotelle Y Department of Organic Chemistry, University of Geneva , Geneva CH-1211, Switzerland.
  • Avestro AJ Department of Organic Chemistry, University of Geneva , Geneva CH-1211, Switzerland.
  • Sakai N Department of Organic Chemistry, University of Geneva , Geneva CH-1211, Switzerland.
  • Matile S Department of Organic Chemistry, University of Geneva , Geneva CH-1211, Switzerland.
  • 2015-09-09
Published in:
  • Journal of the American Chemical Society. - 2015
Alkenes
Amines
Anions
Catalysis
Hydrogen-Ion Concentration
Nitro Compounds
Stereoisomerism
Surface Properties
English Here we provide experimental evidence for anion-π catalysis of enamine chemistry and for asymmetric anion-π catalysis. A proline for enamine formation on one side and a glutamic acid for nitronate protonation on the other side are placed to make the enamine addition to nitroolefins occur on the aromatic surface of π-acidic naphthalenediimides. With increasing π acidity of the formally trifunctional catalysts, rate and enantioselectivity of the reaction increase. Mismatched and more flexible controls reveal that the importance of rigidified, precisely sculpted architectures increases with increasing π acidity as well. The absolute configuration of stereogenic sulfoxide acceptors at the edge of the π-acidic surface has a profound influence on asymmetric anion-π catalysis and, if perfectly matched, affords the highest enantio- and diastereoselectivity.
Language
  • English
Open access status
closed
Identifiers
Persistent URL
https://sonar.ch/global/documents/252395
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