中国科学院上海有机化学研究所机构知识库
Advanced  
SIOC OpenIR  > 金属有机化学国家重点实验室  > 期刊论文
学科主题: 金属有机化学
题名: 1,3-Cationic Alkylidene Migration of Nonclassical Carbocation: A Density Functional Theory Study on Gold(I)-Catalyzed Cycloisomerization of 1,5-Enynes Containing Cyclopropene Moiety
其他题名: 1,3-Cationic Alkylidene Migration of Nonclassical Carbocation: A Density Functional Theory Study on Gold(I)-Catalyzed Cycloisomerization of 1,5-Enynes Containing Cyclopropene Moiety
作者: ZHOU QINGHAI; Li YX(李玉学)
刊名: J. Am. Chem. Soc.
发表日期: 2014
DOI: 10.1021/ja410734e
卷: 136, 期:4, 页:1505-1513
收录类别: SCI
英文摘要: For quite a long time, nonclassical carbocations have only been regarded as special intermediates with limited cases in solvolysis reactions. However, the present work shows that in common reaction, typical nonclassical carbocations may be involved in and have significant effects on the reaction mechanisms. In this work, DFT studies have been performed on the mechanism of gold(I)-catalyzed cycloisomerization of 1,5-enynes containing cyclopropene moiety at PBEIPBE/6-31+G**/SDD level. An unprecedented pathway containing two consecutive 1,3-cationic alkylidene migrations of non-classical carbocation intermediates derived from norbornenyl cation, rather than the generally considered Wagner-Meerwein 1,2-alkyl migrations, was found. Detailed structural analysis shows the nature of this 1,3-cationic alkylidene migration: it is promoted by strong cation-pi interaction between the cationic center and the double bond. Topological analysis shows that for certain nonclassical carbocation intermediates (1c'-A and 1c'-F), there do exist bond critical point and bond path between the cationic center and the double bond. On the basis of the mechanisms proposed, the product selectivity controlled by the substituent effects was also rationalized.
语种: 英语
相关网址: 查看原文
Citation statistics:
内容类型: 期刊论文
URI标识: http://ir.sioc.ac.cn/handle/331003/39032
Appears in Collections:金属有机化学国家重点实验室_期刊论文

Files in This Item: Download All
File Name/ File Size Content Type Version Access License
2014072.pdf(3326KB)期刊论文作者接受稿开放获取View Download

作者单位: 中科院上海有机化学研究所

Recommended Citation:
ZHOU QINGHAI,Li YX. 1,3-Cationic Alkylidene Migration of Nonclassical Carbocation: A Density Functional Theory Study on Gold(I)-Catalyzed Cycloisomerization of 1,5-Enynes Containing Cyclopropene Moiety[J]. J. Am. Chem. Soc.,2014,136(4):1505-1513.
Service
Recommend this item
Sava as my favorate item
Show this item's statistics
Export Endnote File
Google Scholar
Similar articles in Google Scholar
[ZHOU QINGHAI]'s Articles
[李玉学]'s Articles
CSDL cross search
Similar articles in CSDL Cross Search
[ZHOU QINGHAI]‘s Articles
[李玉学]‘s Articles
Related Copyright Policies
Null
Social Bookmarking
Add to CiteULike Add to Connotea Add to Del.icio.us Add to Digg Add to Reddit
文件名: 2014072.pdf
格式: Adobe PDF
此文件暂不支持浏览
所有评论 (0)
暂无评论
 
评注功能仅针对注册用户开放,请您登录
您对该条目有什么异议,请填写以下表单,管理员会尽快联系您。
内 容:
Email:  *
单位:
验证码:   刷新
您在IR的使用过程中有什么好的想法或者建议可以反馈给我们。
标 题:
 *
内 容:
Email:  *
验证码:   刷新

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

 

 

Valid XHTML 1.0!
Powered by CSpace