Nitroxyl-Radical-Catalyzed Oxidative Coupling of Amides with Silylated Nucleophiles through N-Halogenation
Nitroxyl-Radical-Catalyzed Oxidative Coupling of Amides with Silylated Nucleophiles through N-Halogenation
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DOI：
10.1002/anie.201607223
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发表时间：
2016-11-14
影响因子：
16.6
通讯作者：
Togo, Hideo
中科院分区：
文献类型：
--
作者：
Moriyama, Katsuhiko;Kuramochi, Masako;Togo, Hideo
在氮氧自由基的催化下，具有N-保护电子引出基团的胺与硅化亲核试剂发生氧化偶联反应，高产率地提供偶联产物，为有机催化反应开辟了新的前沿。该反应通过N-卤代胺在氮氧基自由基催化剂下的活化，然后与硅烷化亲核试剂进行碳-碳偶联反应进行。对反应机理的研究表明，N-EWG保护的N-卤代酰胺与卤代试剂反应生成的N-卤代胺与氮氧自由基反应生成相应的亚胺。
A nitroxyl-radical-catalyzed oxidative coupling reaction between amines with an N-protecting electron-withdrawing group (EWG) and silylated nucleophiles was developed to furnish coupling products in high yields, thus opening up new frontiers in organocatalyzed reactions. This reaction proceeded through the activation of N-halogenated amides by a nitroxyl-radical catalyst, followed by carbon-carbon coupling with silylated nucleophiles. Studies of the reaction mechanism indicated that the nitroxyl radical activates N-halogenated amides, which are generated from N-EWG-protected amides and a halogenation reagent, to give the corresponding imines.