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Ac loin condensation - Wikipedia, the free enc clopedia

Ac loin condensation
From Wikipedia, the free encyclopedia

Ac loin condensation is a reductive coupling of two carboxylic esters using metallic sodium to
yield an -hydroxyketone, also known as an acyloin.[1][2][3]

The reaction is most successful when is aliphatic and inert. To achieve the condensation, the
reaction is performed in an aprotic solvents with a high boiling point, such as benzene and
toluene. Usage of protic solvents results in the Bouveault-Blanc reduction of the separate esters
rather than condensation. Depending on ring size and steric properties, but independent from
high dilution, the acyloin condensation of diesters favours intramolecular cyclisation over
intermolecular polymerisation.

Contents
1 Mechanism
2 Variations
2.1 Rhlmann-method
3 References
4 See also

Mechanism
The mechanism consists on four steps:
(1) Oxidative ionization of two sodium atoms on the double bond of two ester molecules.
(2) Free radical coupling between two molecules of the homolytic ester derivative (A Wrtz
type coupling). Alkoxy-eliminations in both sides occur, producing a 1,2-diketone.
en.wikipedia.org/wiki/Ac loin_condensationOxidative

ionization
Na Atoms
on carbonyl
bonds
occur
twice
- in 1st
(3) Oxidative ionization of two
sodiumofatoms
on both
diketonedouble
double
bonds.
The
sodium
and 3rd step

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Ac loin condensation - Wikipedia, the free enc clopedia

(3) Oxidative ionization of two sodium atoms on both diketone double bonds. The sodium
enodiolate is formed.
(4) Neutralization with water to form the enodiol, which tautomerizes to acyloin.[4]

Variations
R hlmann-method
The method according to R hlmann[5] employs trimethylchlorosilane as a trapping reagent; by
this, competing reactions are efficiently subdued. Generally, yields increase considerably. The
hydrolytic cleavage of the silylether gives the acyloin. To achieve a mild cleavage methanol can
be used in several cases.

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Ac loin condensation - Wikipedia, the free enc clopedia

Usually toluene, dioxane, tetrahydrofuran or acyclic dialkylethers are employed as solvents.

Advantageously also N-methyl-morpholine has been used. It allowed in some cases a successful
reaction, in which otherwise the reaction failed in less polar media.

Refe ence
1. ^ Bouveault, L., and R. Loquin (1905). "Action du sodium sur les thers des acides monobasiques
fonction simple de la srie grasse" (http://gallica.bnf.fr/ark:/12148/bpt6k30949/f1689.table) .
Comptes. Rendus. 140: 1593 1595. http://gallica.bnf.fr/ark:/12148/bpt6k30949/f1689.table.
2. ^ Finley, K. T. (1964). "The Acyloin Condensation as a Cyclization Method". Chemical Reviews
64 (5): 573 589. doi:10.1021/cr60231a004 (http://dx.doi.org/10.1021%2Fcr60231a004) .
3. ^ Bloomfield, J. J.; Owsley, D. C.; Nelke, J. M. Org. React. 1976, 23.
4. ^ Acyloin condensation (http://www.organic-chemistry.org/namedreactions/acyloincondensation.shtm)
5. ^ Rhlmann K. (1971). "Die Umsetzung von Carbonsureestern mit Natrium in Gegenwart von
Trimethylchlorsilan [Reaction of carboxylic acid esters with sodium in the presence of
trimethylchlorosilane]". S nthesis 1971 (5): 236 253. doi:10.1055/s-1971-21707
(http://dx.doi.org/10.1055%2Fs-1971-21707) .

See al o
Benzoin condensation
Bouveault-Blanc reduction
Claisen condensation
Dieckmann condensation
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Categories:
Condensation reactions Organic redox reactions
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