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Please use this identifier to cite or link to this item: http://hdl.handle.net/123456789/12650

Title: Mechanistic studies on Diels-Alder [4þ2] cycloaddition reactions ofa,b-substituted cyclobutenones: Role of substituents in regio- andstereoselectivity
Authors: Fosu, Evans
Tia, Richard
Adei, Evans
Keywords: Diels-Alder cycloaddition
Mechanism
Regioselectivity
Stereoselectivity
Dane's diene
Cyclobutenone
Issue Date: 3-Nov- 216
Publisher: Elsevier Ltd.
Citation: E. Fosu et al. Mechanistic studies on Diels-Alder [4þ2] cycloaddition reactions ofa,b-substituted cyclobutenones: Role of substituents in regio- andstereoselectivity. http://dx.doi.org/10.1016/j.tet.2016.10.063
Abstract: Diels-Alder reactions of substituted cyclobutenones with 6-methoxy-1-vinyl-3,4-dihydronaphthaleneand methoxy-substituted-1,3-butadiene have been studied with DFT. In the reactions of 6-methoxy-1-vinyl-3,4-dihydronaphthalene with cyclobutenone anda-bromocyclobutenone, the formation of themetaandorthoisomers have the same barriers, indicating that the two isomers might be formed in equalproportions, contrary to earlier reports. The regiochemistry of the reaction is mainly controlled by theketone functionality at C1 on the dienophiles. In the reactions of methoxy-substituted-1,3-butadienewith cyclobutenone anda,b-substituted cyclobutenones theortho/endoandpara/endostereo-isomericpathways are the most favorable pathways, changing toexoselectivity when OH, Br, CH3are placedon theb-carbon of the cyclobutenone, but still withorthoandpararegioselectivity. The stereoselectivityis independent of the bulkiness of substituents. The stability of substituted cycloadducts are lowercompared to unsubstituted adducts and this explains why thea-cyanoketones anda-bromoketoneproducts readily undergotrans-methylation and angular-alkylation as electrophiles.
Description: An article published by Elsevier Ltd and also available at http://dx.doi.org/10.1016/j.tet.2016.10.063
URI: http://hdl.handle.net/123456789/12650
Appears in Collections:College of Science

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