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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
Alternative Title1,3-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)
2014
Source PublicationJ. Am. Chem. Soc.
Volume136Issue:4Pages:1505-1513
AbstractFor 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.
Subject Area金属有机化学
DOI10.1021/ja410734e
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Indexed BySCI
Language英语
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Cited Times:25[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.sioc.ac.cn/handle/331003/39032
Collection金属有机化学国家重点实验室
Affiliation中科院上海有机化学研究所
Recommended Citation
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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