Chiral Bimetallic Catalysts Derived from Chiral Metal Phosphates

Enantioselective Three-Component Asymmetric Aza-Diels-Alder Reactions of Cyclic Ketones

Yongming Deng, Chamini V. Karunaratne, Erika Csatary, David L. Tierney, Kraig Wheeler, Hong Wang

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

A new type of chiral bimetallic catalyst is disclosed. These chiral bimetallic catalysts are easily formed through mixing a metal Lewis acid and a metal binaphthyl phosphate (MLA/M[P]3) in solution. 1H and 31P NMR spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, and X-ray crystallographic analysis reveal a bimetallic structure of the Y(Yb)III/Y[P]3 complexes with bridging binaphthyl phosphate ligands. The Lewis acidity of these chiral bimetallic catalysts is readily tuned by changing either the metal Lewis acid or the chiral metal phosphate. Through cooperative metal Lewis acid-enamine catalysis, asymmetric three-component aza-Diels-Alder reactions of 5-, 6-, and 7-membered cyclic ketones, unsaturated ketoesters, and arylamines were successfully achieved to afford fused bicyclic dihydropyridines in high yields (up to 94%) with high enantioselectivity (up to 99% enantiomeric excess) and excellent chemoselectivity.

Original languageEnglish (US)
Pages (from-to)7984-7993
Number of pages10
JournalJournal of Organic Chemistry
Volume80
Issue number16
DOIs
StatePublished - Aug 21 2015
Externally publishedYes

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Ketones
Lewis Acids
Metals
Phosphates
Catalysts
Dihydropyridines
Enantioselectivity
Acidity
Catalysis
Nuclear magnetic resonance spectroscopy
Ionization
Mass spectrometry
Paramagnetic resonance
Desorption
Spectroscopy
Ligands
X rays
Lasers

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Chiral Bimetallic Catalysts Derived from Chiral Metal Phosphates : Enantioselective Three-Component Asymmetric Aza-Diels-Alder Reactions of Cyclic Ketones. / Deng, Yongming; Karunaratne, Chamini V.; Csatary, Erika; Tierney, David L.; Wheeler, Kraig; Wang, Hong.

In: Journal of Organic Chemistry, Vol. 80, No. 16, 21.08.2015, p. 7984-7993.

Research output: Contribution to journalArticle

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abstract = "A new type of chiral bimetallic catalyst is disclosed. These chiral bimetallic catalysts are easily formed through mixing a metal Lewis acid and a metal binaphthyl phosphate (MLA/M[P]3) in solution. 1H and 31P NMR spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, and X-ray crystallographic analysis reveal a bimetallic structure of the Y(Yb)III/Y[P]3 complexes with bridging binaphthyl phosphate ligands. The Lewis acidity of these chiral bimetallic catalysts is readily tuned by changing either the metal Lewis acid or the chiral metal phosphate. Through cooperative metal Lewis acid-enamine catalysis, asymmetric three-component aza-Diels-Alder reactions of 5-, 6-, and 7-membered cyclic ketones, unsaturated ketoesters, and arylamines were successfully achieved to afford fused bicyclic dihydropyridines in high yields (up to 94{\%}) with high enantioselectivity (up to 99{\%} enantiomeric excess) and excellent chemoselectivity.",
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