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258:. Aldehydes are reduced before ketones allowing for a measure of control over the reaction. If it is necessary to reduce one carbonyl in the presence of another, the common carbonyl protecting groups may be employed. Groups, such as alkenes and alkynes, that normally pose a problem for reduction by other means have no reactivity under these conditions.
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have shown high yields and high stereoselectivity in the reduction of carbonyls to alcohols. The ruthenium catalyst has been shown, however, to go through a ruthenium hydride intermediate. The
Meerwein–Ponndorf–Verley reduction has also been effected with synthetically useful yield by plutonium (III)
410:
Several problems restrict the use of the
Meerwein–Ponndorf–Verley reduction compared to the use of other reducing agents. The stereochemical control is seriously limited. Often a large amount of aluminium alkoxide is needed when using commercial reagent, and there are several known side reactions.
326:
The use of an intramolecular MPV reduction can give good enantiopurity. By tethering the ketone to the hydride source only one transition state is possible (Figure 4) leading to the asymmetric reduction. This method, however, has the ability to undergo the reverse
116:
catalysis in the presence of a sacrificial alcohol. The advantages of the MPV reduction lie in its high chemoselectivity and its use of a cheap environmentally friendly metal catalyst. MPV reductions have been described as "obsolete" owing to the development of
331:
due to the proximity of the two reagents. Thus the reaction runs under thermodynamic equilibrium with the ratio of the products related to their relative stabilities. After the reaction is run the hydride-source portion of the molecule can be removed.
372:
source of chirality. The low selectivity of this method is attributed to the shape of the transition state. It has been shown that the transition state is a planar six member transition state. This is different than the believed
290:) in the reduction of 2-chloroacetophenone. This enantioselection is due to the sterics of the two phenol groups in the six membered transition state as shown in Figure 3. In Figure 3, 1 is favored over 2 due to the large
414:
While commercial aluminium isopropoxide is available, the use of it often requires catalyst loadings of up to 100-200 mol%. This hinders the use of the MPV reduction on scale. Aluminium alkoxides made in situ from
233:
Each step in the cycle is reversible. The reaction is driven by the thermodynamic properties of the intermediates and the products. Several other mechanisms have been proposed for this reaction, including a
274:
alcohols. The three main ways to achieve the asymmetric reduction is by use of a chiral alcohol hydride source, use of an intramolecular MPV reduction, or use of a chiral ligand on the aluminium alkoxide.
936:
K. Haack; S. Hashiguchi; A. Fujii; T. Ikariya; R. Noyori (1997). "The
Catalyst Precursor, Catalyst, and Intermediate in the RuII-Promoted Asymmetric Hydrogen Transfer between alcohols and Ketones".
773:
M. Fujita; Y. Takarada; T. Sugimura, A. Tai (1997). "Reliable chiral transfer through thermodynamic equilibrium of the intramolecular
Meerwein–Ponndorf–Verley reduction and Oppenauer oxidation".
667:
R. Cohen; C. R. Graves; S. T. Nguyen, J. M. L. Martin & M. A. Ratner (2004). "The
Mechanism of Aluminum-Catalyzed Meerwein-Schmidt-Ponndorf-Verley Reduction of Carbonyls to alcohols".
419:
reagents have far better activity requiring as little as 10% loading. The activity difference is believed to be due to the large aggregation state of the commercially available product.
627:
Wolfgang
Ponndorf (1926). "Der reversible Austausch der Oxydationsstufen zwischen Aldehyden oder Ketonen einerseits und primären oder sekundären Alkoholen anderseits".
994:
212:
909:
D. A. Evans; S. G. Nelson; M. R. Gagne; A. R. Muci (1993). "A Chiral
Samarium-Based Catalyst for the Asymmetric Meerwein–Ponndorf–Verley Reduction".
669:
128:
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T. Ooi; T. Miura; K. Marouka (1998). "Highly
Efficient, Catalytic Meerwein–Ponndorf–Verler Reduction with a Novel Bidentate Aluminum Catalyst".
751:
278:
One method of achieving the asymmetric MPV reduction is with the use of chiral hydride donating alcohols. The use of chiral alcohol (R)-(+)-
75:
1046:
305:
364:
on the aluminium alkoxide can affect the stereochemical outcome of the MPV reduction. This method lead to the reduction of substituted
581:
560:
796:
E. J. Campbell; H. Zhou; S. T. Nguyen (2002). "The
Asymmetric Meerwein-Schmidt-Ponndorf-Verley Reduction of Prochiral Ketones with
813:
384:
1041:
872:
C. R. Graves; K. A. Scheidt; S. T. Nguyen (2006). "Enantioselective MSPV Reduction of
Ketimines Using 2-propanol and (BINOL)Al".
339:
157:
and ethanol could reduce aldehydes to their alcohols. Ponndorf applied the reaction to ketones and upgraded the catalyst to
60:
835:
E. J. Campbell; H. Zhou; S. T. Nguyen (2001). "Catalytic Meerwein-Pondorf-Verley Reduction by Simple Aluminum Complexes".
1008:
G.K. Chuah; S. Jaenicke; Y.Z. Zhu; S.H. Liu (2006). "Meerwein–Ponndorf–Verley reduction over Heterogeneous Catalysts".
608:
Verley, A. (1925). "Exchange of functional groups between two molecules. Exchange of alcohol and aldehyde groups".
68:
963:
Benjamin P. Warner, Joseph A. D’Alessio, Arthur N. Morgan III; d'Alessio; Morgan; Burns; Schake; Watkin (2000).
711:; Huskens, J. (1994). "Meerwein-Ponndorf-Verley Reductions and Oppenauer Oxidations: An Integrated Approach".
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using a chiral alkoxide. The addition of a phosphinoyl group to the nitrogen of the ketimine allowed for high
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374:
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The standard MPV reduction is a homogeneous reaction several heterogeneous reactions have been developed.
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44:
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in up to 83%ee (Figure 5). The appeal of this method is that it uses a chiral ligand as opposed to a
201:. Finally, an alcohol from solution displaces the newly reduced carbonyl to regenerate the catalyst
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Brown, Herbert C.; Ramachandran, P. Veeraraghavan (1996). "Sixty Years of Hydride Reductions".
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197:. At this point the new carbonyl dissociates and gives the tricoordinated aluminium species
174:
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Several side reactions are known to occur. In the case of ketones and especially aldehydes
181:, a carbonyl oxygen is coordinated to achieve the tetra coordinated aluminium intermediate
874:
837:
511:
173:
The MPV reduction is believed to go through a catalytic cycle involving a six-member ring
141:
Figure 1, Exchange of carbonyl oxidation states in the presence of aluminium isopropoxide.
579:; Schmidt, Rudolf (1925). "Ein neues Verfahren zur Reduktion von Aldehyden und Ketonen".
642:
980:
514:(1944). "Reduction with Aluminum Alkoxides (The Meerwein-Ponndorf-Verley Reduction)".
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10.1002/(SICI)1521-3773(19980918)37:17<2347::AID-ANIE2347>3.0.CO;2-U
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The Meerwein–Ponndorf–Verley reduction has been used in the synthesis of chiral
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The MPV reduction was independently discovered by Albert Verley and the team of
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The aluminium based Meerwein–Ponndorf–Verley reduction can be performed on
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10.1002/1521-3773(20020315)41:6<1020::AID-ANIE1020>3.0.CO;2-S
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One of the great draws of the Meerwein–Ponndorf–Verley reduction is its
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the hydride is transferred to the carbonyl from the alkoxy ligand via a
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have been observed. Aldehydes with no α-hydrogens can undergo the
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Figure 3, Transition states of MPV reduction with a chiral alcohol
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Reduction of ketones and aldehydes to their corresponding alcohols
965:"Plutonium(III)-catalyzed Meerwein –Ponndorf –Verley reactions"
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Figure 2, Catalytic cycle of Meerwein–Ponndorf–Verley reduction
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transfer is supported by experimental and theoretical data.
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as shown in Figure 2. Starting with the aluminium alkoxide
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Figure 4, Transition state of intramolecular MPV reduction
153:
and Rudolf Schmidt in 1925. They found that a mixture of
547:. ACS Symposium Series. Vol. 641. pp. 1–30.
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Meerwein–Ponndorf–Verley reduction with chiral alcohol
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Meerwein–Ponndorf–Verley reduction with chiral ligand
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238:mechanism as well as a mechanism involving an
286:-bromophen-ethyl alcohol gave 82%ee (percent
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800:PrOH Catalyzed by Al Catalysts".
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