Quantum Chemical Studies of Lewis-Acid Catalyzed Organic Chemical Reactions

被引：0
作者：
Sakata K. [1 ]
机构：
[1] Faculty of Pharmaceutical Sciences, Toho University, 2-2-1 Miyama, Funabashi
来源：
Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry | 2022年 / 80卷 / 02期
关键词：
Lewis-acid catalyst; quantum chemical calculations;
D O I：
10.5059/yukigoseikyokaishi.80.103
中图分类号：
学科分类号：
摘要：
Lewis-acid catalyst is one of the most fundamental catalysts in organic chemical reactions. In this paper, our recent quantum chemical studies on Lewis-acid catalyzed organic chemical reactions have been presented. First, we focused on the mechanism of Lewis-acid activated Lewis acid catalysts. Then, the normal-electron-demand Diels-Alder reaction between cyclopentadiene and maleic anhydride was discussed in order to clarify the origin of the stereoselectivity. The endo selectivity is attained when dienophile carries a group （or groups） involving highly polarized bonds. We show that the well-known donor-acceptor relationship in the normal-electron-demand Diels-Alder reaction is linked to the endo selectivity. On the basis of the results, the Diels-Alder reaction of cyclopentadiene with methyl acrylate catalyzed by a simple Lewis acid, AlCl3, has been investigated. The Lewis-acid catalyst facilitates the cycloaddition and brings a higher endo selectivity in the highly asynchronous process. Finally, we discussed two reactions catalyzed by tris（pentafluorophenyl）borane, B（C6F5）3 © 2022 Society of Synthetic Organic Chemistry. All rights reserved.
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页码：115 / 125
页数：10
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