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 language | English |
|---|---|
| Pages (from-to) | 11582-11585 |
| Number of pages | 4 |
| Journal | Journal of the American Chemical Society |
| Volume | 137 |
| Issue number | 36 |
| Early online date | 8 Sep 2015 |
| DOIs | |
| Publication status | Published - 16 Sep 2015 |
Keywords
- Alkenes/chemistry
- Amines/chemistry
- Anions
- Catalysis
- Hydrogen-Ion Concentration
- Nitro Compounds/chemistry
- Stereoisomerism
- Surface Properties
