Dynamic structural change of the self-assembled lanthanum complex induced by lithium triflate for direct catalytic asymmetric aldol-Tishchenko reaction

Yoshihiro Horiuchi, Vijay Gnanadesikan, Takashi Ohshima, Hyuma Masu, Kosuke Katagiri, Yoshihisa Sei, Kentaro Yamaguchi, Masakatsu Shibasaki

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Abstract

The development of a direct catalytic asymmetric aldol-Tishchenko reaction and the nature of its catalyst are described. An aldol-Tishchenko reaction of various propiophenone derivatives with aromatic aldehydes was promoted by [LaLi3(binol)3] (LLB), and reactivity and enantioselectivity were dramatically enhanced by the addition of lithium trifluoromethanesulfonate (LiOTf). First, we observed a dynamic structural change of LLB by the addition of LiOTf using 13C NMR spectroscopy, electronspray ionization mass spectrometry (ESI-MS), and cold-spray ionization mass spectrometry (CSI-MS). X-ray crystallography revealed that the structure of the newly generated self-assembled complex was a binuclear [La 2Li4(binaphthoxide)5] complex 6. A reverse structural change of complex 6 to LLB by the addition of one equivalent of Li2(binol) was also confirmed by ESI-MS and experimental results. The drastic concentration effects on the direct catalytic asymmetric aldol-Tishchenko reaction suggested that the addition of LiOTf to LLB generated an active oligomeric catalyst species.

Original languageEnglish
Pages (from-to)5195-5204
Number of pages10
JournalChemistry - A European Journal
Volume11
Issue number18
DOIs
Publication statusPublished - Sep 5 2005
Externally publishedYes

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Lanthanum
Structural dynamics
Lithium
Ionization
Mass spectrometry
Propiophenones
Catalysts
Enantioselectivity
X ray crystallography
Aldehydes
Nuclear magnetic resonance spectroscopy
Derivatives
trifluoromethanesulfonic acid
3-hydroxybutanal

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

Cite this

Dynamic structural change of the self-assembled lanthanum complex induced by lithium triflate for direct catalytic asymmetric aldol-Tishchenko reaction. / Horiuchi, Yoshihiro; Gnanadesikan, Vijay; Ohshima, Takashi; Masu, Hyuma; Katagiri, Kosuke; Sei, Yoshihisa; Yamaguchi, Kentaro; Shibasaki, Masakatsu.

In: Chemistry - A European Journal, Vol. 11, No. 18, 05.09.2005, p. 5195-5204.

Research output: Contribution to journalArticle

Horiuchi, Yoshihiro ; Gnanadesikan, Vijay ; Ohshima, Takashi ; Masu, Hyuma ; Katagiri, Kosuke ; Sei, Yoshihisa ; Yamaguchi, Kentaro ; Shibasaki, Masakatsu. / Dynamic structural change of the self-assembled lanthanum complex induced by lithium triflate for direct catalytic asymmetric aldol-Tishchenko reaction. In: Chemistry - A European Journal. 2005 ; Vol. 11, No. 18. pp. 5195-5204.
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