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DFT-Guided Phosphoric-Acid-Catalyzed Atroposelective Arene Functionalization of Nitrosonaphthalene
Chem ( IF 23.5 ) Pub Date : 2020-06-23 , DOI: 10.1016/j.chempr.2020.06.001
Wei-Yi Ding , Peiyuan Yu , Qian-Jin An , Katherine L. Bay , Shao-Hua Xiang , Shaoyu Li , Ying Chen , K.N. Houk , Bin Tan

Functionalization of arenes represents the most efficient approach for constructing a core backbone of important aryl compounds. Compared with the well-developed electrophilic aromatic substitution and transition-metal-catalyzed C–H activation, nucleophilic aromatic substitution remains challenging because of the lack of a convenient route for rapid conversion of the σH adduct to other stable and versatile intermediates in situ. Guided by computational design, we were able to realize asymmetric nucleophilic aromatic substitution by introducing a nitroso group on naphthalene via chiral phosphoric acid catalysis. This strategy enables efficient construction of atropisomeric indole-naphthalenes and indole-anilines with excellent stereocontrol. Density functional theory (DFT) calculations provide further insights into the origins of enantioselectivity and the reaction mechanisms. The successful application in the synthesis of NOBINs (2-amino-2′-hydroxy-1,1′-binaphthyl) extends the utility of this strategy.



中文翻译:

DFT引导下的磷酸催化硝基萘的Atroposelective Arene功能化

芳烃的官能化代表构建重要的芳基化合物的核心骨架的最有效方法。与发达电芳族取代和过渡金属催化的C-H活化,相比亲核芳香取代遗体由于缺乏对于σ的快速转换一个方便的途径的挑战ħ加合物到其他稳定和通用中间体原位。在计算设计的指导下,我们能够通过手性磷酸催化在萘上引入亚硝基来实现不对称的亲核芳族取代。该策略使得能够以优异的立体控制有效地构建阻转异构的吲哚-萘和吲哚-苯胺。密度泛函理论(DFT)计算为对映选择性的起源和反应机理提供了进一步的见解。在合成NOBINs(2-氨基-2'-羟基-1,1'-联萘基)方面的成功应用扩展了该策略的实用性。

更新日期:2020-06-23
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