Direct catalytic asymmetric aldol-Tishchenko reaction

Vijay Gnanadesikan, Yoshihiro Horiuchi, Takashi Ohshima, Masakatsu Shibasaki

Research output: Contribution to journalArticle

88 Citations (Scopus)

Abstract

A direct catalytic asymmetric aldol reaction of propionate equivalent was achieved via the aldol-Tishchenko reaction. Coupling an irreversible Tishchenko reaction to a reversible aldol reaction overcame the retro-aldol reaction problem and thereby afforded the products in high enantio and diastereoselectivity using 10 mol % of the asymmetric catalyst. A variety of ketones and aldehydes, including propyl and butyl ketones, were coupled efficiently, yielding the corresponding aldol-Tishchenko products in up to 96% yield and 95% ee. Diastereoselectivity was generally below the detection limit of 1H NMR (>98:2). Preliminary studies performed to clarify the mechanism revealed that the aldol products were racemic with no diastereoselectivity. On the other hand, the Tishchenko products were obtained in a highly enantiocontrolled manner.

Original languageEnglish
Pages (from-to)7782-7783
Number of pages2
JournalJournal of the American Chemical Society
Volume126
Issue number25
DOIs
Publication statusPublished - Jun 30 2004
Externally publishedYes

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Ketones
Aldehydes
Nuclear magnetic resonance
Catalysts
Propionates
Limit of Detection
3-hydroxybutanal

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Direct catalytic asymmetric aldol-Tishchenko reaction. / Gnanadesikan, Vijay; Horiuchi, Yoshihiro; Ohshima, Takashi; Shibasaki, Masakatsu.

In: Journal of the American Chemical Society, Vol. 126, No. 25, 30.06.2004, p. 7782-7783.

Research output: Contribution to journalArticle

Gnanadesikan, Vijay ; Horiuchi, Yoshihiro ; Ohshima, Takashi ; Shibasaki, Masakatsu. / Direct catalytic asymmetric aldol-Tishchenko reaction. In: Journal of the American Chemical Society. 2004 ; Vol. 126, No. 25. pp. 7782-7783.
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