Hu Mengjie, Liang Yuchen, Ru Liying, Ye Sheng, Zhang Lei, Huang Xin, Bao Ming, Kong Lichun, Peng Bo
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004, China.
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116023, China.
Angew Chem Int Ed Engl. 2023 Sep 4;62(36):e202306914. doi: 10.1002/anie.202306914. Epub 2023 Jul 27.
Owing to its unique physical properties, fluorine is often used to open up new reaction channels. In this report, we establish a cooperation of [5,5]-rearrangement and fluorine-assisted temporary dearomatization for arene multi-functionalization. Specifically, the [5,5]-rearrangement of fluoroaryl sulfoxides with β,γ-unsaturated nitriles generates an intriguing dearomatized sulfonium species which is short-lived but exhibits unusually high electrophilicity and thus can be instantly trapped by nucleophiles and dienes at a remarkably low temperature (-95 °C) to produce four types of valuable multi-functionalized benzenes, respectively, involving appealing processes of defluorination, desulfurization, and sulfur shift. Mechanistic studies indicate that the use of fluorine on arenes not only circumvents the generally inevitable [3,3]-rearrangement but also impedes the undesired rearomatization process, thus provides a precious space for constructing and elaborating the temporarily dearomatized fluorinated sulfonium species.
由于其独特的物理性质，氟常被用于开辟新的反应通道。在本报告中，我们建立了[5,5]重排与氟辅助的芳烃临时去芳构化之间的协同作用，以实现芳烃的多功能化。具体而言，氟代芳基亚砜与β,γ-不饱和腈的[5,5]重排生成了一种有趣的去芳构化锍物种，该物种寿命短暂，但具有异常高的亲电性，因此可以在极低温度（-95°C）下被亲核试剂和二烯迅速捕获，分别生成四种有价值的多功能化苯，涉及脱氟、脱硫和硫迁移等引人关注的过程。机理研究表明，在芳烃上使用氟不仅避免了通常不可避免的[3,3]重排，还阻碍了不期望的再芳构化过程，从而为构建和阐述临时去芳构化的氟化锍物种提供了宝贵的空间。
