ISL OpenIR  > 青海盐湖研究所知识仓储
Effect of electron-withdrawing group on the [3,3]-sigmatropic rearrangements of 1,5-enynes, 1,5-diynes and 1,2-diene-5-ynes: A theoretical study
Xia, Yuanzhi2,3; Zhou, Fengying1; Li, Yahong1,2; Lia, Wu2
2009-06-30
发表期刊JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM
卷号904期号:1-3页码:69-73
文章类型Article
摘要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.
关键词Cope Rearrangement Electronic Effect Theoretical Calculation Activation Barrier Reaction Energy
WOS标题词Science & Technology ; Physical Sciences
关键词[WOS]TRANSITION-STATE GEOMETRIES ; QUANTUM-MECHANICAL METHODS ; DENSITY-FUNCTIONAL THEORY ; ACID-CATALYZED REACTIONS ; AB-INITIO CALCULATIONS ; COPE REARRANGEMENT ; THERMAL REARRANGEMENT ; CLAISEN REARRANGEMENTS ; PERICYCLIC-REACTIONS ; HARTREE-FOCK
收录类别SCI
语种英语
WOS研究方向Chemistry
WOS类目Chemistry, Physical
WOS记录号WOS:000266512600011
引用统计
文献类型期刊论文
条目标识符http://ir.isl.ac.cn/handle/363002/5882
专题青海盐湖研究所知识仓储
作者单位1.Suzhou Univ, Coll Chem & Chem Engn, Key Lab Organ Synth Jiangsu Prov, Suzhou 215123, Peoples R China
2.Chinese Acad Sci, Qinghai Inst Salt Lakes, CAS Key Lab Salt Lake Resources & Chem, Xining 810008, Peoples R China
3.Chinese Acad Sci, Grad Sch, Beijing 100039, Peoples R China
推荐引用方式
GB/T 7714
Xia, Yuanzhi,Zhou, Fengying,Li, Yahong,et al. Effect of electron-withdrawing group on the [3,3]-sigmatropic rearrangements of 1,5-enynes, 1,5-diynes and 1,2-diene-5-ynes: A theoretical 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]-sigmatropic rearrangements of 1,5-enynes, 1,5-diynes and 1,2-diene-5-ynes: A theoretical 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]-sigmatropic rearrangements of 1,5-enynes, 1,5-diynes and 1,2-diene-5-ynes: A theoretical study".JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM 904.1-3(2009):69-73.
条目包含的文件
条目无相关文件。
个性服务
推荐该条目
保存到收藏夹
查看访问统计
导出为Endnote文件
谷歌学术
谷歌学术中相似的文章
[Xia, Yuanzhi]的文章
[Zhou, Fengying]的文章
[Li, Yahong]的文章
百度学术
百度学术中相似的文章
[Xia, Yuanzhi]的文章
[Zhou, Fengying]的文章
[Li, Yahong]的文章
必应学术
必应学术中相似的文章
[Xia, Yuanzhi]的文章
[Zhou, Fengying]的文章
[Li, Yahong]的文章
相关权益政策
暂无数据
收藏/分享
所有评论 (0)
暂无评论
 

除非特别说明,本系统中所有内容都受版权保护,并保留所有权利。