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	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
	ZHOU QINGHAI; Li YX(李玉学)
刊名	J. Am. Chem. Soc.
	2014
卷号	136期号:4页码:1505-1513
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
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.
学科主题	金属有机化学
收录类别	SCI
原文出处	http://dx.doi.org/10.1021/ja410734e
语种	英语
内容类型	期刊论文
源URL	[http://ir.sioc.ac.cn/handle/331003/39032]
专题	上海有机化学研究所_金属有机化学国家重点实验室
作者单位	中科院上海有机化学研究所
推荐引用方式 GB/T 7714	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.
APA	ZHOU QINGHAI,&李玉学.(2014).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. Am. Chem. Soc.,136(4),1505-1513.
MLA	ZHOU QINGHAI,et al."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. Am. Chem. Soc. 136.4(2014):1505-1513.

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