6533b827fe1ef96bd12867a4
RESEARCH PRODUCT
Understanding the mechanism of stereoselective synthesis of cyclopentenes via N-heterocyclic carbene catalyzed reactions of enals with enones.
Ramón J. ZaragozáManuel ArnóLuis R. Domingosubject
Bicyclic moleculeStereochemistryOrganic ChemistryEtherBiochemistrychemistry.chemical_compoundchemistryNucleophileIntramolecular forceAlkoxy groupCyclopentenePhysical and Theoretical ChemistryCarbeneEnonedescription
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 CO(2) elimination, the final trans-cyclopentene.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2010-08-27 | Organicbiomolecular chemistry |