Triptycenyl Sulfide: A Practical and Active Catalyst for Electrophilic Aromatic Halogenation using N-Halosuccinimides,Journal of the American Chemical Society

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Triptycenyl Sulfide: A Practical and Active Catalyst for Electrophilic Aromatic Halogenation using N-Halosuccinimides
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-12-23 , DOI: 10.1021/jacs.9b12672
Yuji Nishii ₁ , Mitsuhiro Ikeda ₂ , Yoshihiro Hayashi ₃ , Susumu Kawauchi ₃ , Masahiro Miura ₂

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A Lewis base catalyst Trip-SMe (Trip = triptycenyl) for electrophilic aromatic halogenation using N-halosuccinimides (NXS) is introduced. In the presence of an appropriate activator (as a non-coordinating-anion source), a series of unactivated aromatic compounds were halogenated at ambient temperature using NXS. This catalytic system was applicable to transformations that are currently unachievable except for the use of Br2 or Cl2: e.g. multi-halogenation of naphthalene, regioselective bromination of BINOL, etc. Controlled experiments revealed that the triptycenyl substituent exerts a crucial role for the catalytic activity, and kinetic experiments implied the occurrence of a sulfonium salt [Trip-S(Me)Br][SbF6] as an active species. Compared to simple dialkyl sulfides, Trip-SMe exhibited a significant charge-separated ion pair character within the halonium complex whose structural information was obtained by the single-crystal X-ray analysis. A preliminary computational study disclosed that the π system of the triptycenyl functionality is a key motif to consolidate the enhancement of electrophilicity.

中文翻译：

三烯硫醚：一种实用的活性催化剂，用于使用 N-卤代琥珀酰亚胺进行亲电芳香族卤化

介绍了一种用于使用 N-卤代琥珀酰亚胺 (NXS) 进行亲电芳香卤化的路易斯碱催化剂 Trip-SMe（Trip = triptycenyl）。在合适的活化剂（作为非配位阴离子源）存在下，一系列未活化的芳香族化合物在环境温度下使用 NXS 进行卤化。该催化体系适用于目前除使用 Br2 或 Cl2 之外无法实现的转化：例如萘的多卤化、BINOL 的区域选择性溴化等。对照实验表明，三烯基取代基对催化活性起着至关重要的作用，和动力学实验暗示锍盐 [Trip-S(Me)Br][SbF6] 作为活性物质的存在。与简单的二烷基硫醚相比，Trip-SMe 在卤络合物中表现出显着的电荷分离离子对特征，其结构信息是通过单晶 X 射线分析获得的。一项初步的计算研究表明，三烯基官能团的 π 系统是巩固亲电性增强的关键基序。

更新日期：2019-12-23

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