In-plane aromaticity in 1,3-dipolar cycloadditions. solvent effects, selectivity, and nucleus-independent chemical shifts

被引:233
作者
Cossío, FP
Morao, I
Jiao, HJ
Schleyer, PV
机构
[1] Euskal Herriko Unibertsitatea, Kimika Fakultatea, San Sebastian, Spain
[2] Univ Erlangen Nurnberg, Inst Organ Chem, D-91054 Erlangen, Germany
关键词
D O I
10.1021/ja9831397
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The aromaticity and the regiochemistry of several 1,3-dipolar cycloadditions have been studied computationally. It is found that all the transition structures associated with concerted supra-supra processes are in-plane aromatic, and this aromaticity is compatible with a ring current circulating along the molecular plane. Solvent effects enhance the activation barrier of the reaction and diminish its synchronicity, with little impact on aromaticity. According to our calculations,aromaticity is important but does not determine the regiochemistry of the reaction. Other phenomena such as electrostatic interactions and solvent effects can modify the regiochemical and the stereochemical outcome.
引用
收藏
页码:6737 / 6746
页数:10
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