Schleyer Hyperconjugative Aromaticity and Diels-Alder Reactivity of 5-Substituted Cyclopentadienes
Schleyer Hyperconjugative Aromaticity and Diels-Alder Reactivity of 5-Substituted Cyclopentadienes
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DOI：
10.1002/jcc.24191
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发表时间：
2016-01-05
影响因子：
3
通讯作者：
Houk, K. N.
中科院分区：
文献类型：
--
作者：
Levandowski, Brian J.;Zou, Lufeng;Houk, K. N.
Schleyer对5-取代环戊二烯超共轭芳香性和抗芳香性的发现进一步扩展了我们对芳香性普遍影响的认识。受体通过施莱耶负超共轭芳香性诱导反芳香性，而给体则相反。计算了5-取代环戊二烯与乙烯和马来酸酐的Diels-Alder反应性。5-取代环戊二烯与乙烯或马来酸酐的Diels-Alder反应的室温气相速率常数的预测差异是由过渡态畸变能的差异引起的，这与这些分子的超共轭芳构性直接相关。(C) 2015 Wiley期刊公司
Schleyer's discovery of hyperconjugative aromaticity and antiaromaticity in 5-substituted cyclopentadienes further expanded our understanding of the pervasive influence of aromaticity. Acceptors induce antiaromatic character by Schleyer's negative hyperconjugative aromaticity, and donors have the opposite effect. We computationally explored the Diels-Alder reactivity of 5-substituted cyclopentadienes with ethylene and maleic anhydride. The predicted billionfold difference in the computed gas phase rate constants at room temperature for the Diels-Alder reactions of 5-substituted cyclopentadienes with ethylene or maleic anhydride results from differences in the transition state distortion energies, which are directly related to the hyperconjugative aromaticity of these molecules. (C) 2015 Wiley Periodicals, Inc.