Escape from Palladium: Nickel-Catalyzed Catellani Annulation.
Escape from Palladium: Nickel-Catalyzed Catellani Annulation.
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DOI：
10.1021/jacs.3c03780
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发表时间：
2023-05
影响因子：
15
通讯作者：
Jingfeng Huo;Yue Fu;Melody J Tang;P. Liu;Guangbin Dong
中科院分区：
文献类型：
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作者：
Jingfeng Huo;Yue Fu;Melody J Tang;P. Liu;Guangbin Dong
虽然Catellani反应对于芳烃官能化变得越来越重要，但它们仅由钯催化。在这里，我们报告了第一个镍催化的芳基三氟甲磺酸酯和氯化物的Catellani型成环，形成各种苯并环丁烯稠合降冰片烷在高效率。机制研究揭示了一个令人惊讶的外层协调金属化/去质子化途径在形成的镍镧，以及基本的作用的基础和三氟甲磺酸根阴离子。与相应的钯催化剂相比，该反应显示出宽的官能团耐受性和增强的区域选择性。
While Catellani reactions have become increasingly important for arene functionalizations, they have been solely catalyzed by palladium. Here we report the first nickel-catalyzed Catellani-type annulation of aryl triflates and chlorides to form various benzocyclobutene-fused norbornanes in high efficiency. Mechanistic studies reveal a surprising outer-sphere concerted metalation/deprotonation pathway during the formation of the nickelacycle, as well as the essential roles of the base and the triflate anion. The reaction shows a broad functional group tolerance and enhanced regioselectivity compared to the corresponding palladium catalysis.