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Electrooxidative iridium-catalyzed sp2 C–H activation–annulation leading to cationic π-extended heteroaromatics
Organic Chemistry Frontiers ( IF 4.6 ) Pub Date : 2024-07-12 , DOI: 10.1039/d4qo01019a
Qi-Liang Yang 1 , Na-Na Guo 1 , Shu-Xian Liu 1 , Bei-Ning Zhang 1 , Guodong Zou 2 , Hai-Xia Wang 1 , Dong-Chao Wang 1 , Hai-Ming Guo 1
Affiliation  

This study demonstrates an electrochemically driven, Ir(III)-catalyzed method for pyridine-, azo-, and purine-directed olefinic and aromatic C(sp2)–H activation and regioselective annulation with alkynes for the synthesis of biologically useful quaternary ammonium salts. This approach notably eliminates the need for stoichiometric amounts of external oxidants, offering a broader substrate scope along with improved product regioselectivity under mild electrolysis conditions as compared to previously employed strong oxidant conditions. Detailed mechanistic insights, including the isolation, characterization, and cyclovoltammetric analysis of catalytically relevant iridium(III) and iridium(I) intermediates, provided strong supporting evidence for an Ir(III/I) catalytic cycle operation.

中文翻译:


电氧化铱催化 sp2 C-H 活化-成环,产生阳离子 π-扩展杂芳烃



本研究展示了一种电化学驱动的 Ir(III) 催化方法,用于吡啶、偶氮和嘌呤定向的烯烃和芳香族 C(sp 2 )–H 活化以及与炔烃的区域选择性环化合成生物学上有用的季铵盐。该方法显着消除了对化学计量量的外部氧化剂的需求,与以前采用的强氧化剂条件相比,在温和电解条件下提供了更广泛的底物范围以及改进的产物区域选择性。详细的机理见解,包括催化相关铱 (III) 和铱 () 中间体的分离、表征和循环伏安分析,为 Ir(III/) 催化循环操作提供了强有力的支持证据。
更新日期:2024-07-17
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