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 CH2 Cl2 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
