铁催化重氮化合物选择性地正式插入炔丙醇的C(sp)-C(sp)键：通向炔基取代的全碳季碳中心。
Fe-Catalyzed Selective Formal Insertion of Diazo Compounds into C(sp)-C(sp) Bonds of Propargyl Alcohols: Access to Alkyne-Substituted All-Carbon Quaternary Centers.
作者信息
Wang Dong-Kai, Li Liu-Bin, Liu Fa-Liang, Qiu Hui, Li Jiao-Zhe, Zhang Jianfeng, Deng Chao, Wei Wen-Ting
机构信息
School of Materials Science and Chemical Engineering, Key Laboratory of Advanced Mass Spectrometry and Molecular Analysis of Zhejiang Province, Ningbo University, Ningbo, Zhejiang 315211, P. R. China.
Jiangsu Key Laboratory of Pesticide Science and Department of Chemistry, College of Sciences, Nanjing Agricultural University, Nanjing, Jiangsu 210095, P. R. China.
出版信息
ACS Cent Sci. 2022 Jul 27;8(7):1028-1034. doi: 10.1021/acscentsci.2c00204. Epub 2022 Jul 11.
The construction of all-carbon quaternary centers, especially those containing an alkyne-substituted framework, represents an important challenge in organic synthesis. Here we present a novel Fe-catalyzed selective formal insertion of diazo compounds into C(sp)-C(sp) bonds of propargyl alcohols under mild conditions that enables the streamlined construction of alkyne-substituted all-carbon quaternary centers. This unique strategy starts with in situ generation of an ester group in the presence of carboxylic acids, followed by insertion of metal-carbene into C(sp)-C(sp) bonds, which may open up a new reaction mode for exploring metal-carbene insertion into acyclic C-C bonds.
构建全碳季中心，尤其是那些含有炔烃取代骨架的全碳季中心，是有机合成中的一项重要挑战。在此，我们展示了一种新型铁催化反应，即在温和条件下将重氮化合物选择性地正式插入到炔丙醇的C(sp)-C(sp)键中，从而能够简化构建炔烃取代的全碳季中心。这种独特的策略始于在羧酸存在下原位生成酯基，随后将金属卡宾插入C(sp)-C(sp)键中，这可能为探索金属卡宾插入非环状C-C键开辟一种新的反应模式。
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