The mechanisms of gallium-catalysed skeletal rearrangement of1,6-enyneseInsights from quantum mechanical computations

Simple item page
dc.contributor.authorBorketey, Joseph Bortey
dc.contributor.authorOpoku, Ernest
dc.contributor.authorTia, Richard
dc.contributor.authorAdei, Evans
dc.date.accessioned2020-07-08T14:41:24Z
dc.date.accessioned2023-04-19T02:07:29Z
dc.date.available2020-07-08T14:41:24Z
dc.date.available2023-04-19T02:07:29Z
dc.date.issued2019-10-10
dc.descriptionAn article published by Elsevier Inc. and also available at https://doi.org/10.1016/j.jmgm.2019.107476en_US
dc.description.abstractThe transition metal-catalysed skeletal reorganization of 1,6-enynes can lead to three types of productsea typeIproduct occurring via the cleavage of the alkene CeC bonds and the migration of the terminalalkene carbon to the terminus of the alkyne; a typeIIproduct arising from cleavage of both the doubleand the triple bonds followed by insertion of the terminal alkene carbon into the alkyne CeC triple bond;and a typeIIIproduct which is obtained when there is a cleavage of the olefinic bond followed byformation of two new bonds from each carbon to each of the acetylenic carbons. The course of thesereactions is highly dependent on the metal catalyst used and type of substitution at the alkene andalkyne moieties of the enyne. In this mechanistic study of the re-organization of 1,6-enynes catalysed byGaCl3, performed at the DFT M06/6-311G(d,p) level of theory, the parent reaction selectively leads to theformation of the typeIproduct through the formation of the open cyclopropane ring. The presence ofsubstituents at the acetylenic moiety governs the preferred position of the metal along the alkyne bondwithin the pi-complex: with electron-withdrawing groups (EWGs), the metal prefers the terminal carbonwhile electron-donating groups (EDGs) lead to the metal preferring the internal carbon. EWGs at thealkyne moiety efficiently favour the formation of the typeIproduct. Substituents at the olefin moietyalter the mechanism of the reaction which may favour the selective formation of the typeIorIIIproductdepending on the type of substituent. EWGs at the olefinic moiety favour formation of the typeIIIproduct when the alkyne moiety is unsubstituted whiles EDGs forms the typeIproduct selectively.Solvent and temperature have no substantial effects on the energetic trends and product distribution.Hence, gas-phase calculations are deemed adequate for the problem at hand.en_US
dc.description.sponsorshipKNUSTen_US
dc.identifier.citationJ.B. Borketey et al. / Journal of Molecular Graphics and Modelling 94 (2020) 107476, https://doi.org/10.1016/j.jmgm.2019.107476en_US
dc.identifier.urihttps://ir.knust.edu.gh/handle/123456789/12663
dc.language.isoenen_US
dc.publisherElsevier Incen_US
dc.subjectSkeletal reorganizationen_US
dc.subject1,6-Enynesen_US
dc.subjectGallium catalysisen_US
dc.subjectCycloisomerizationen_US
dc.subjectPost-transition metalen_US
dc.subjectMechanistic studyen_US
dc.titleThe mechanisms of gallium-catalysed skeletal rearrangement of1,6-enyneseInsights from quantum mechanical computationsen_US
dc.typeArticleen_US
Files
Original bundle
Now showing 1 - 1 of 1
Thumbnail Image
Name:
2019Borketeyet.al2019JMGM.pdf
Size:
1.44 MB
Format:
Adobe Portable Document Format
Description:
Download
License bundle
Now showing 1 - 2 of 2
Thumbnail Image
Name:
license.txt
Size:
1.73 KB
Format:
Item-specific license agreed to upon submission
Description:
Download
Thumbnail Image
Name:
license.txt
Size:
1.71 KB
Format:
Item-specific license agreed to upon submission
Description:
Download
Collections
Articles