Copper-Catalyzed Cascade Transformation of Homopropargyl Azides into Trifluoromethylated Nitriles via C-C Cleavage
Copper-Catalyzed Cascade Transformation of Homopropargyl Azides into Trifluoromethylated Nitriles via C-C Cleavage
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铜催化叠氮均炔通过 C-C 裂解级联转化为三氟甲基化腈
DOI：
10.1021/acs.orglett.7b00571
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发表时间：
2017
期刊：
影响因子：
5.2
通讯作者：
Liu Pei-Nian
中科院分区：
文献类型：
--
作者：
Chen Shuang;Li Deng-Yuan;Jiang Liang-Liang;Liu Kai;Liu Pei-Nian
在Cu催化剂存在下，叠氮高炔丙基的级联反应得到了3-三氟甲基丁-3-烯腈，具有良好的产率和区域选择性。该反应似乎是第一次将高炔丙基叠氮化物直接转化为三氟甲基化腈。机理研究表明，该转化过程是通过将CF 3自由基加成到炔上、通过1，4-芳基迁移进行C-C裂解以及形成腈来进行的。该方案提供了一种新的策略，通过自由基迁移衍生的C-C裂解将叠氮化物转化为腈。
A cascade reaction of homopropargyl azides in the presence of a Cu catalyst was achieved, affording 3-(trifluoromethyl)but-3-enenitriles with good yields and excellent regioselectivity. This reaction appears to be the first direct conversion of homopropargyl azides into trifluoromethylated nitriles. Mechanistic studies indicate that the transformation proceeds by addition of a CF3radical to the alkyne, C–C cleavage by 1,4-aryl radical migration, and nitrile formation. This protocol provides a novel strategy for transforming azides into nitriles via C–C cleavage derived from radical migration.