Enantioselective Diels-Alder reaction of α-Acyloxyacroleins catalyzed by chiral 1,1′-binaphthyl-2,2′-diammonium salts

Akira Sakakura, Kenji Suzuki, Kazuaki Ishihara

Research output: Contribution to journalArticle

77 Citations (Scopus)

Abstract

A diammonium salt of chiral 1,1′-binaphthyl-2,2′-diamine (2a) and trifluoromethanesulfonimide (Tf2NH) shows excellent catalytic activity and enantioselectivity for the Diels-Alder reaction of α-acyloxyacroleins. For example, in the presence of 5 mol% of 2a and 9.5 mol% of Tf2NH, the Diels-Alder reaction of α- (cyclohexanecarbonyloxy)acrolein with cyclopentadiene proceeded in EtCN at -75 °C to give the adducts in 88% yield with 92% exo and 91 % ee. The electron-donating property of the acyl group of the α-acyloxyacroleins increases the enantioselectivity due to the formation of strong intramolecular hydrogen bonding of the acyl group with a proton of the ammonium group in the transition state. This catalyst can be easily prepared in situ by mixing the commercially available chiral diamine and Tf2NH.

Original languageEnglish
Pages (from-to)2457-2465
Number of pages9
JournalAdvanced Synthesis and Catalysis
Volume348
Issue number16-17
DOIs
Publication statusPublished - Nov 2006
Externally publishedYes

Fingerprint

Diamines
Enantioselectivity
Salts
Acrolein
Cyclopentanes
Ammonium Compounds
Protons
Catalyst activity
Hydrogen bonds
Catalysts
Electrons

Keywords

  • α-acyloxyacrolein
  • 1,1′-binaphthyl-2,2′- diamine
  • Ammonium salts
  • Cycloaddition
  • Diels-Alder reaction

ASJC Scopus subject areas

  • Chemistry (miscellaneous)
  • Organic Chemistry
  • Catalysis

Cite this

Enantioselective Diels-Alder reaction of α-Acyloxyacroleins catalyzed by chiral 1,1′-binaphthyl-2,2′-diammonium salts. / Sakakura, Akira; Suzuki, Kenji; Ishihara, Kazuaki.

In: Advanced Synthesis and Catalysis, Vol. 348, No. 16-17, 11.2006, p. 2457-2465.

Research output: Contribution to journalArticle

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N2 - A diammonium salt of chiral 1,1′-binaphthyl-2,2′-diamine (2a) and trifluoromethanesulfonimide (Tf2NH) shows excellent catalytic activity and enantioselectivity for the Diels-Alder reaction of α-acyloxyacroleins. For example, in the presence of 5 mol% of 2a and 9.5 mol% of Tf2NH, the Diels-Alder reaction of α- (cyclohexanecarbonyloxy)acrolein with cyclopentadiene proceeded in EtCN at -75 °C to give the adducts in 88% yield with 92% exo and 91 % ee. The electron-donating property of the acyl group of the α-acyloxyacroleins increases the enantioselectivity due to the formation of strong intramolecular hydrogen bonding of the acyl group with a proton of the ammonium group in the transition state. This catalyst can be easily prepared in situ by mixing the commercially available chiral diamine and Tf2NH.

AB - A diammonium salt of chiral 1,1′-binaphthyl-2,2′-diamine (2a) and trifluoromethanesulfonimide (Tf2NH) shows excellent catalytic activity and enantioselectivity for the Diels-Alder reaction of α-acyloxyacroleins. For example, in the presence of 5 mol% of 2a and 9.5 mol% of Tf2NH, the Diels-Alder reaction of α- (cyclohexanecarbonyloxy)acrolein with cyclopentadiene proceeded in EtCN at -75 °C to give the adducts in 88% yield with 92% exo and 91 % ee. The electron-donating property of the acyl group of the α-acyloxyacroleins increases the enantioselectivity due to the formation of strong intramolecular hydrogen bonding of the acyl group with a proton of the ammonium group in the transition state. This catalyst can be easily prepared in situ by mixing the commercially available chiral diamine and Tf2NH.

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