Azolium/Hydroquinone Organo‐Radical Co‐Catalysis: Aerobic C?C‐Bond Cleavage in Ketones
Azolium/Hydroquinone Organo‐Radical Co‐Catalysis: Aerobic C?C‐Bond Cleavage in Ketones
复制标题
唑鎓/氢醌有机自由基共催化：酮中的有氧 C?C 键断裂
DOI：
10.1002/chem.202004943
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Takemoto Yoshiji
中科院分区：
文献类型：
--
作者：
Nakatsuji Yuya;Kobayashi Yusuke;Masuda Sakyo;Takemoto Yoshiji
有机自由基催化剂近年来引起了人们极大的兴趣，该领域的发展有望拓宽有机催化的应用。在本文中，报道了不需要任何光照射、自由基引发剂或预活化底物的自由基产生体系的第一个实例。使用唑鎓盐和对苯二酚作为助催化剂实现了2-取代环己酮的氧化C-C-键断裂。基于扩散有序光谱和循环伏安法测量以及计算研究的结果，提出了催化机理。
Organo‐radical catalysts have recently attracted great interest, and the development of this field can be expected to broaden the applications of organocatalysis. Herein, the first example of a radical‐generating system is reported that does not require any photoirradiation, radical initiators, or preactivated substrates. The oxidative C−C‐bond cleavage of 2‐substituted cyclohexanones was achieved using an azolium salt and a hydroquinone as co‐catalysts. A catalytic mechanism was proposed based on the results of diffusion‐ordered spectroscopy and cyclic voltammetry measurements, as well as computational studies.