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NHC-Boryl Radical Catalysis for Cycloisomerization With C–C Triple Bond Reorganization
CCS Chemistry ( IF 11.2 ) Pub Date : 2019-10-21 , DOI: 10.31635/ccschem.019.20190025
Ai-Qing Xu 1 , Feng-Lian Zhang 1 , Tian Ye 1 , Zhi-Xiang Yu 2 , Yi-Feng Wang 1, 3
Affiliation  

Our present study unveils a new and efficient N-heterocyclic carbene (NHC)-boryl radical-catalyzed cycloisomerization of N-(2-ethynylaryl)arylamides. This catalytic process is triggered by the addition of an NHC-boryl radical to the alkynyl moiety, followed by a radical cascade comprising of an intramolecular cyclization, successive 1,5- and 1,2-aryl migrations, and the reorganization of a C–C triple bond. Eventually, the catalytic cycle is achieved through a radical β-fragmentation reaction, from which the starting NHC-boryl radical is regenerated, and a structurally important quinolinone framework is assembled. A 13C-labeling experiment was carried out to verify the C–C triple bond reorganization, and the proposed catalytic pathway was supported further by density functional theory calculations. Our identification of NHC-boryl radical as a catalyst, as well as its mode of operation via radical addition/elimination mechanism, would stimulate the advancement of design of radical catalysis and the discovery of novel enantioselective radical-catalyzed processes.

中文翻译:

NHC-硼自由基催化CC-C三键重组进行环异构化

我们目前的研究揭示了一种新型和有效的N-(2-乙炔基芳基)芳基酰胺的N-杂环卡宾(NHC)-硼自由基催化的环异构化。此催化过程是通过在炔基部分添加NHC-硼基自由基,然后进行自由基级联反应而引发的,该级联反应包括分子内环化,连续的1,5-和1,2-芳基迁移以及C–的重组C三键。最终,通过自由基β-片段化反应实现催化循环,从该自由基β-片段化反应中再生出起始的NHC-硼烷基,并组装了结构上重要的喹啉酮骨架。进行了13C标记实验以验证C-C三键重组,并且密度泛函理论计算进一步支持了所提出的催化途径。
更新日期:2020-06-24
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