Catalytic Meerwein-Ponndorf-Verley (MPV) and Oppenauer (OPP) reactions: Remarkable acceleration of the hydride transfer by powerful bidentate aluminum alkoxides

Takashi Ooi, Tomoya Miura, Yoshifumi Itagaki, Hayato Ichikawa, Keiji Maruoka

Research output: Contribution to journalReview articlepeer-review

72 Citations (Scopus)

Abstract

A highly efficient catalytic procedure for Meerwein-Ponndorf-Verley (MPV) reduction has been devised by employing (2,7-dimethyl-1,8-biphenylenedioxy)bis(dialkoxyaluminum) (3) as a catalyst. For example, reduction of 4-phenylcyclohexanone in CH2Cl2 with i-PrOH (1 equiv) as a hydride source in the presence of a catalytic amount of the in situ generated 3a (1 mol%) smoothly proceeded at room temperature within 1 hour to furnish 4-phenylcyclohexanol in 82% isolated yield. In sharp contrast, the conventional MPV reduction with stoichiometric Al(i-PrO)3 resulted in the recovery of the starting ketone under similar conditions. Our approach also enabled the reverse reaction of MPV reduction, i.e., Oppenauer (OPP) oxidation in a truly catalytic manner. Furthermore, these findings prompted us to develop a simultaneous intramolecular reduction/oxidation of hydroxy carbonyl substrates via the MPV reaction process in the presence of bidentate aluminum catalyst 1, where highly chemoselective hydride transfer from a secondary alcohol moiety to the remote carbonyl group took place. Finally, we demonstrate that the modern MPV system is applicable to high-speed, catalytic Tishchenko reactions. For instance, the dimerization product of cyclohexanecarbaldehyde was obtained in almost quantitative yield using only 0.2 mol% of catalyst 3a. Based on this result, highly stereoselective intramolecular Tishchenko reduction of a β-hydroxy ketone was also accomplished successfully.

Original languageEnglish
Pages (from-to)279-291
Number of pages13
JournalSynthesis
Issue number2
DOIs
Publication statusPublished - 2002
Externally publishedYes

Keywords

  • Alcohols
  • Bidentate aluminum alkoxides
  • Carbonyl compounds
  • Meerwein-Ponndorf-Verley (MPV) reduction
  • Oppenauer (OPP) oxidation
  • Tishchenko reaction

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

Fingerprint

Dive into the research topics of 'Catalytic Meerwein-Ponndorf-Verley (MPV) and Oppenauer (OPP) reactions: Remarkable acceleration of the hydride transfer by powerful bidentate aluminum alkoxides'. Together they form a unique fingerprint.

Cite this