ISL OpenIR  > 青海盐湖研究所知识仓储
Effect of electron-withdrawing group on the [3,3]-sigmatropicrearrangements of 1,5-enynes, 1,5-diynes and 1,2-diene-5-ynes: Atheoretical study
Xia, Yuanzhi; Zhou, Fengying; Li, Yahong; Lia, Wu
2009
Source PublicationJOURNAL OF MOLECULAR STRUCTURE-THEOCHEM
ISSN0166-1280
Volume904Issue:1-3Pages:69-73
Contribution RankSCI
KeywordCope Rearrangement Electronic Effect Theoretical Calculation
LanguageThe electronic effects of an electron-withdrawing group (exemplified by formyl group) on the kinetic and thermodynamic aspects of substituted 1,5-enyne. 1,5-diyne, and 1,2-diene-5-yne Cope rearrangements were investigated by means of DFT and CBS-QB3 calculations. The energy barriers of the formyl substituted reactions are lower than those of the unsubstituted ones almost in all cases, and the barriers will be further lowered when catalyzed by ACl(3), The most obvious electronic effect was calculated for the C-2 formyl substituted 1,5-enyne rearrangements, which have activation barriers of 27.1 and 18.1 kcal/mol, respectively, for the uncatalyzed and catalyzed reactions. The charge transfer induced by the electron-withdrawing group and stabilization of the charge by Lewis acid are responsible for the different energetic profiles. The formyl substitution will change the thermodynamic profiles of the transformations, notablely, increase the reaction enthalpies of the 1,5-diyne and 1,2-diene-5-yne rearrangements by over 5.0 kcal/mol, as result of the stabilization effect of a formyl substitution attached directly to the unsaturated moieties of the products. (c) 2009 Elsevier B.V. All rights reserved. The electronic effects of an electron-withdrawing group (exemplified by formyl group) on the kinetic and thermodynamic aspects of substituted 1,5-enyne. 1,5-diyne, and 1,2-diene-5-yne Cope rearrangements were investigated by means of DFT and CBS-QB3 calculations. The energy barriers of the formyl substituted reactions are lower than those of the unsubstituted ones almost in all cases, and the barriers will be further lowered when catalyzed by ACl(3), The most obvious electronic effect was calculated for the C-2 formyl substituted 1,5-enyne rearrangements, which have activation barriers of 27.1 and 18.1 kcal/mol, respectively, for the uncatalyzed and catalyzed reactions. The charge transfer induced by the electron-withdrawing group and stabilization of the charge by Lewis acid are responsible for the different energetic profiles. The formyl substitution will change the thermodynamic profiles of the transformations, notablely, increase the reaction enthalpies of the 1,5-diyne and 1,2-diene-5-yne rearrangements by over 5.0 kcal/mol, as result of the stabilization effect of a formyl substitution attached directly to the unsaturated moieties of the products. (c) 2009 Elsevier B.V. All rights reserved.
Document Type期刊论文
Identifierhttp://ir.isl.ac.cn/handle/363002/2102
Collection青海盐湖研究所知识仓储
Recommended Citation
GB/T 7714
Xia, Yuanzhi,Zhou, Fengying,Li, Yahong,et al. Effect of electron-withdrawing group on the [3,3]-sigmatropicrearrangements of 1,5-enynes, 1,5-diynes and 1,2-diene-5-ynes: Atheoretical study[J]. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,2009,904(1-3):69-73.
APA Xia, Yuanzhi,Zhou, Fengying,Li, Yahong,&Lia, Wu.(2009).Effect of electron-withdrawing group on the [3,3]-sigmatropicrearrangements of 1,5-enynes, 1,5-diynes and 1,2-diene-5-ynes: Atheoretical study.JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM,904(1-3),69-73.
MLA Xia, Yuanzhi,et al."Effect of electron-withdrawing group on the [3,3]-sigmatropicrearrangements of 1,5-enynes, 1,5-diynes and 1,2-diene-5-ynes: Atheoretical study".JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM 904.1-3(2009):69-73.
Files in This Item:
There are no files associated with this item.
Related Services
Recommend this item
Bookmark
Usage statistics
Export to Endnote
Google Scholar
Similar articles in Google Scholar
[Xia, Yuanzhi]'s Articles
[Zhou, Fengying]'s Articles
[Li, Yahong]'s Articles
Baidu academic
Similar articles in Baidu academic
[Xia, Yuanzhi]'s Articles
[Zhou, Fengying]'s Articles
[Li, Yahong]'s Articles
Bing Scholar
Similar articles in Bing Scholar
[Xia, Yuanzhi]'s Articles
[Zhou, Fengying]'s Articles
[Li, Yahong]'s Articles
Terms of Use
No data!
Social Bookmark/Share
All comments (0)
No comment.
 

Items in the repository are protected by copyright, with all rights reserved, unless otherwise indicated.