Polarity-Reversal Strategy for the Functionalization of Electrophilic Strained Molecules via Light-Driven Cobalt Catalysis
Polarity-Reversal Strategy for the Functionalization of Electrophilic Strained Molecules via Light-Driven Cobalt Catalysis
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DOI：
10.1021/jacs.0c00245
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发表时间：
2020-03-18
影响因子：
15
通讯作者：
Gryko, Dorota
中科院分区：
文献类型：
--
作者：
Ociepa, Michal;Wierzba, Aleksandra J.;Gryko, Dorota
应变释放驱动的方法学是获得结构基序的强大工具，非常受制药行业的欢迎。弹簧负载的环状试剂的反应性主要取决于它们固有的亲电反应性的转化。在这里，我们提出了一种基于光驱动钴催化的极性反转策略，该策略能够通过菌株释放来产生亲核自由基。设计了两种不同类型的反应：Giese型加成反应和Co/Ni催化的交叉偶联反应，证明了该方法的适用性。此外，一系列的电化学、光谱和动力学实验以及对中间体烷基钴(III)络合物的X-射线结构分析使人们对反应机理有了更深入的了解。
Strain-release-driven methodology is a powerful tool for accessing structural motifs, highly desirable by the pharmaceutical industry. The reactivity of spring-loaded cyclic reagents is dominated by transformations relying on their inherent electrophilic reactivity. Herein, we present a polarity-reversal strategy based on light-driven cobalt catalysis, which enables the generation of nucleophilic radicals through strain release. The applicability of this methodology is demonstrated by the design of two distinct types of reactions: Giese-type addition and Co/Ni-catalyzed cross-coupling. Moreover, a series of electrochemical, spectroscopic, and kinetic experiments as well as X-ray structural analysis of the intermediate alkylcobalt(III) complex give deeper insight into the mechanism of the reaction.