Chiral rare earth organophosphates as homogeneous Lewis acid catalysts for the highly enantioselective hetero-Diels-Alder reactions

Hiroshi Furuno, Tetsuji Hayano, Takeshi Kambara, Yuichi Sugimoto, Takeshi Hanamoto, Yumiko Tanaka, Yong Zhi Jin, Takumi Kagawa, Junji Inanaga

Research output: Contribution to journalArticle

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Abstract

Various trivalent rare earth-chiral phosphate complexes [(R)-1-RE, (R)-3-RE, and (R)-4-Ce] were prepared and evaluated as a Lewis acid catalyst for the asymmetric hetero-Diels-Alder reaction of aldehydes with the Danishefsky's diene. Some of them effectively promoted the reaction at room temperature in the presence or absence of achiral additives under homogeneous conditions to afford the corresponding cycloadducts with high ee's (up to 99% ee). During these reactions, remarkably high asymmetric amplifications (positive nonlinear effects) were observed as the first example in the metal ion-chiral ligand 1:3 catalytic system. A scandium catalyst bearing the H 8-BNP ligand, (R)-3-Sc, could be recovered after the reaction and successfully reused for the next round of reactions. In addition, the hetero-Diels-Alder reaction of α-keto esters was effectively catalyzed by the ytterbium complex, (R)-1-Yb, without any additives thus producing the asymmetric quaternary carbon in excellent enantioselectivities (up to >99% ee).

Original languageEnglish
Pages (from-to)10509-10523
Number of pages15
JournalTetrahedron
Volume59
Issue number52
DOIs
Publication statusPublished - Dec 22 2003

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Lewis Acids
Organophosphates
Cycloaddition Reaction
Rare earths
Bearings (structural)
Scandium
Ytterbium
Ligands
Catalysts
Enantioselectivity
Aldehydes
Metal ions
Amplification
Esters
Carbon
Metals
Phosphates
Ions
Temperature

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Cite this

Chiral rare earth organophosphates as homogeneous Lewis acid catalysts for the highly enantioselective hetero-Diels-Alder reactions. / Furuno, Hiroshi; Hayano, Tetsuji; Kambara, Takeshi; Sugimoto, Yuichi; Hanamoto, Takeshi; Tanaka, Yumiko; Jin, Yong Zhi; Kagawa, Takumi; Inanaga, Junji.

In: Tetrahedron, Vol. 59, No. 52, 22.12.2003, p. 10509-10523.

Research output: Contribution to journalArticle

Furuno, H, Hayano, T, Kambara, T, Sugimoto, Y, Hanamoto, T, Tanaka, Y, Jin, YZ, Kagawa, T & Inanaga, J 2003, 'Chiral rare earth organophosphates as homogeneous Lewis acid catalysts for the highly enantioselective hetero-Diels-Alder reactions', Tetrahedron, vol. 59, no. 52, pp. 10509-10523. https://doi.org/10.1016/j.tet.2003.06.011
Furuno, Hiroshi ; Hayano, Tetsuji ; Kambara, Takeshi ; Sugimoto, Yuichi ; Hanamoto, Takeshi ; Tanaka, Yumiko ; Jin, Yong Zhi ; Kagawa, Takumi ; Inanaga, Junji. / Chiral rare earth organophosphates as homogeneous Lewis acid catalysts for the highly enantioselective hetero-Diels-Alder reactions. In: Tetrahedron. 2003 ; Vol. 59, No. 52. pp. 10509-10523.
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