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

Yingjie Zhao, Yoann Cotelle, Alyssa-Jennifer Avestro, Naomi Sakai, Stefan Matile

Research output: Contribution to journalArticlepeer-review

Abstract

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.

Original languageEnglish
Pages (from-to)11582-11585
Number of pages4
JournalJournal of the American Chemical Society
Volume137
Issue number36
Early online date8 Sept 2015
DOIs
Publication statusPublished - 16 Sept 2015

Keywords

  • Alkenes/chemistry
  • Amines/chemistry
  • Anions
  • Catalysis
  • Hydrogen-Ion Concentration
  • Nitro Compounds/chemistry
  • Stereoisomerism
  • Surface Properties

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