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Synthesis 2002(2): 0279-0291
DOI: 10.1055/s-2002-19802
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart · New York

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*
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan
Fax: +81(75)7534000; e-Mail: maruoka@kuchem.kyoto-u.ac.jp;
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Publication History

Received 26 August 2001
Publication Date:
03 August 2004 (online)

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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.

Key words

Meerwein-Ponndorf-Verley (MPV) reduction - Oppenauer (OPP) oxidation - bidentate aluminum alkoxides - carbonyl compounds - Tishchenko reaction - alcohols