Copper‐Catalyzed Intramolecular Oxidative Amination of Unactivated Internal Alkenes |
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| Authors: | Peng Xiong Fan Xu Xiang‐Yang Qian Yared Yohannes Dr. Jinshuai Song Prof. Dr. Xin Lu Prof. Dr. Hai‐Chao Xu |
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| Affiliation: | 1. Collaborative Innovation Center of Chemistry for Energy Material, State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, Xiamen University, Xiamen, P. R. China;2. Fujian Institute of Research on Structure of Matter, Chinese Academy of Sciences, Fuzhou, P. R. China;3. Web:http://chem.xmu.edu.cn/groupweb/hcxu/ 0000-0002-3008-5143 Collaborative Innovation Center of Chemistry for Energy Material, State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, Xiamen University, Xiamen, P. R. China |
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| Abstract: | A copper‐catalyzed oxidative amination of unactivated internal alkenes has been developed. The Wacker‐type oxidative alkene amination reaction is traditionally catalyzed by a palladium through a mechanism involving aminopalladation and β‐hydride elimination. Replacing the precious and scarce palladium with a cheap and abundant copper for this transformation has been challenging because of the difficulty associated with the aminocupration of internal alkenes. The combination of a simple copper salt, without additional ligand, as the catalyst and Dess–Martin periodinane as the oxidant, promotes efficiently the oxidative amination of allylic carbamates and ureas bearing di‐ and trisubstituted alkenes leading to oxazolidinones and imidazolidinones. Preliminary mechanistic studies suggested a hybrid radical–organometallic mechanism involving an amidyl radical cyclization to form the key C?N bond. |
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| Keywords: | copper cyclization oxidation radicals synthetic methods |
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