Understanding the mechanism of stereoselective synthesis of cyclopentenes viaN-heterocyclic carbene catalyzed reactions of enals with enones

文献情報

出版日 2010-08-26

DOI 10.1039/C0OB00088D

インパクトファクター 3.876

著者

Luis R. Domingo, Ramón J. Zaragozá, Manuel Arnó

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要旨

The N-heterocyclic carbene (NHC) catalyzed addition of enals to enones to yield trans-cyclopentenes has been investigated using DFT methods at B3LYP/6-31G** computational level. This NHC catalyzed reaction comprises several steps. The first one is the formation of a Breslow intermediate, which nucleophilically attacks to the conjugated position of the enone to yield an enol-enolate. This second step is responsible for the trans relationship at the final cyclopentene. An intramolecular aldolic condensation allows for the formation of the alkoxy cyclopentane intermediate, that by intramolecular nucleophilic attack on the carbonyl group yields a bicyclic ether. The extrusion of the NHC catalyst affords a bicyclic lactone, yielding by CO2 elimination, the final trans-cyclopentene.

掲載誌

Organic & Biomolecular Chemistry

CiteScore: 3.4

自己引用率: 10.3%

年間論文数: 1041

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