Publication Date:
2012-12-06
Description:
The intramolecular asymmetric Michael addition reaction catalyzed by imidazolidinone is investigated using the density functional theory calculations. The details of the reaction mechanism, potential energy surfaces, and the influence of the acid additive are investigated. The reaction process includes two stages. The first stage is Michael addition , in which the enamine complex is created and then the Michael addition is carried out. The second stage is a product separation stage which includes an enol-keto tautomerization and a two-step hydrolysis . The enantioselectivity is controlled by the Michael addition step which involves a new carbon–carbon bond formation . The calculation results provide a general model which may explain the mechanism and enantioselectivity of the title reaction. Copyright © 2012 John Wiley & Sons, Ltd. The imidazolidinone salt catalyst and aldehyde form an enamine intermediate. The enamine intermediate and α, β -unsaturated ketone form the intramolecular Michael addition product. Last, the addition product is hydrolyzed, which leads to the formation of product and regenerate imidazolidinone catalyst. The enantioselectivity is controlled by the Michael addition step which involves a carbon–carbon bond formation step.
Print ISSN:
0894-3230
Electronic ISSN:
1099-1395
Topics:
Chemistry and Pharmacology
,
Physics
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