Asymmetric catalysis with self-organized chiral lanthanum complexes: Practical and highly enantioselective epoxidation of α,β-unsaturated ketones

Kazuhiro Daikai, Tetsuji Hayano, Rie Kino, Hiroshi Furuno, Takumi Kagawa, Junji Inanaga

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

A highly efficient and practical method for obtaining α,β-epoxy ketones with high optical purities was developed. The chiral lanthanum complex self-organized in situ from lanthanum triisopropoxide, (R)-BINOL, triarylphosphine oxide, and alkyl hydroperoxide (1:1:1:1) was found to catalyze the epoxidation of α,β-unsaturated ketones with tert-butyl hydroperoxide or cumene hydroperoxide at room temperature to give the corresponding epoxy ketones in high enantioselectivities (up to >99% enantiomeric excess (ee)). A remarkably high asymmetric amplification, a positive nonlinear effect, was observed in the epoxidation of chalcone, which strongly suggests the formation of a dinuclear peroxide-involved p-complex as the active catalyst.

Original languageEnglish
Pages (from-to)83-88
Number of pages6
JournalChirality
Volume15
Issue number1
DOIs
Publication statusPublished - Jan 7 2003

Fingerprint

Lanthanum
Epoxidation
Ketones
Catalysis
Chalcone
tert-Butylhydroperoxide
Enantioselectivity
Peroxides
Oxides
Hydrogen Peroxide
Amplification
Catalysts
Temperature

All Science Journal Classification (ASJC) codes

  • Analytical Chemistry
  • Catalysis
  • Pharmacology
  • Drug Discovery
  • Spectroscopy
  • Organic Chemistry

Cite this

Asymmetric catalysis with self-organized chiral lanthanum complexes : Practical and highly enantioselective epoxidation of α,β-unsaturated ketones. / Daikai, Kazuhiro; Hayano, Tetsuji; Kino, Rie; Furuno, Hiroshi; Kagawa, Takumi; Inanaga, Junji.

In: Chirality, Vol. 15, No. 1, 07.01.2003, p. 83-88.

Research output: Contribution to journalArticle

Daikai, Kazuhiro ; Hayano, Tetsuji ; Kino, Rie ; Furuno, Hiroshi ; Kagawa, Takumi ; Inanaga, Junji. / Asymmetric catalysis with self-organized chiral lanthanum complexes : Practical and highly enantioselective epoxidation of α,β-unsaturated ketones. In: Chirality. 2003 ; Vol. 15, No. 1. pp. 83-88.
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