Copper-Catalyzed Aerobic Autoxidation of N-Hydroxycarbamates Probed by Mass Spectrometry
文献类型：期刊论文
| 作者 | Xie, Xiaobo1; Zhang, Long2; He, Qing1; Hou, Jian1; Xu, Changming2; Zhang, Ning1; Luo, Sanzhong2; Nie, Zongxiu1,3 |
| 刊名 | CHEMISTRY-A EUROPEAN JOURNAL
 |
| 出版日期 | 2015-10-05 |
| 卷号 | 21期号:41页码:14630-14637 |
| 关键词 | autoxidation copper mass spectrometry reaction mechanisms reactive intermediates |
| 英文摘要 | We present herein a mechanistic investigation by nanoelectrospray ionization mass spectrometry of copper-catalyzed aerobic oxidative processes involved in the N-nitrosocarbonyl aldol reaction of N-hydroxycarbamates. Protonated amine and copper as charge-tags aided the detection of reaction intermediates, which verified the enamine mechanism together with a competing enol process. Our experimental results reveal that the copper-catalyzed aerobic oxidation of N-hydroxycarbamates may proceed through an autoxidation catalytic mechanism in which a CbzNHOC radical abstracts a hydrogen from the bound N-hydroxycarbamate to release the nitroso intermediate through a bimolecular hydrogen-atom transfer. In this process, the chiral diamine also works as a ligand for copper to facilitate the aerobic oxidative step. The dual role of the chiral vicinal diamine as both an aminocatalyst and a bidentate ligand was finally uncovered. |
| 收录类别 | SCI |
| 语种 | 英语 |
| 公开日期 | 2016-05-09 |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/29134]  |
| 专题 | 化学研究所_活体分析化学实验室 |
| 作者单位 | 1.Chinese Acad Sci, Inst Chem, Beijing Natl Lab Mol Sci, Key Lab Analyt Chem Living Biosyst, Beijing 100190, Peoples R China 2.Chinese Acad Sci, Key Lab Mol Recognit & Funct, Beijing Natl Lab Mol Sci, Inst Chem, Beijing 100190, Peoples R China 3.Natl Ctr Mass Spectrometry Beijing BNLMS, Beijing 100190, Peoples R China |
| 推荐引用方式 GB/T 7714 | Xie, Xiaobo,Zhang, Long,He, Qing,et al. Copper-Catalyzed Aerobic Autoxidation of N-Hydroxycarbamates Probed by Mass Spectrometry[J]. CHEMISTRY-A EUROPEAN JOURNAL,2015,21(41):14630-14637. |
| APA | Xie, Xiaobo.,Zhang, Long.,He, Qing.,Hou, Jian.,Xu, Changming.,...&Nie, Zongxiu.(2015).Copper-Catalyzed Aerobic Autoxidation of N-Hydroxycarbamates Probed by Mass Spectrometry.CHEMISTRY-A EUROPEAN JOURNAL,21(41),14630-14637. |
| MLA | Xie, Xiaobo,et al."Copper-Catalyzed Aerobic Autoxidation of N-Hydroxycarbamates Probed by Mass Spectrometry".CHEMISTRY-A EUROPEAN JOURNAL 21.41(2015):14630-14637. |
入库方式： OAI收割
来源：化学研究所
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