| Tuning the Reactivity of Radical through a Triplet Diradical Cu(II) Intermediate in Radical Oxidative Cross-Coupling | |
| Department | OSSO国家重点实验室 |
Zhou, Liangliang1; Yi, Hong1; Zhu, Lei3; Qi, Xiaotian3; Jiang, Hanpeng4; Liu, Chao1 ; Feng, Yuqi4; Lan, Yu3; Lei AW(雷爱文)1,2; Lei AW(雷爱文)
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| 2015 | |
| Source Publication | Scientific Reports
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| ISSN | 2045-2322 |
| Volume | 5Pages:15934(1-12) |
| Abstract | Highly selective radical/radical cross-coupling is paid more attention in bond formations. However, due to their intrinsic active properties, radical species are apt to achieve homo-coupling instead of cross-coupling, which makes the selective cross-coupling as a great challenge and almost untouched. Herein a notable strategy to accomplish direct radical/radical oxidative cross-coupling has been demonstrated, that is metal tuning a transient radical to a persistent radical intermediate followed by coupling with another transient radical. Here, a transient nitrogen-centered radical is tuned to a persistent radical complex by copper catalyst, followed by coupling with a transient allylic carbon-centered radical. Firstly, nitrogen-centered radical generated from N-methoxybenzamide stabilized by copper catalyst was successfully observed by EPR. Then DFT calculations revealed that a triplet diradical Cu(II) complex formed from the chelation N-methoxybenzamide nitrogen-centered radical to Cu(II) is a persistent radical species. Moreover, conceivable nitrogen-centered radical Cu(II) complex was observed by high-resolution electrospray ionization mass spectrometry (ESI-MS). Ultimately, various allylic amides derivatives were obtained in good yields by adopting this strategy, which might inspire a novel and promising landscape in radical chemistry. |
| Subject Area | 物理化学与绿色催化 |
| DOI | 10.1038/srep15934 |
| Funding Organization | the 973 Program (2012CB725302);the National Natural Science Foundation of China (21390400;21272180;21302148);the Research Fund for the Doctoral Program of Higher Education of China (20120141130002);the Ministry of Science and Technology of China (2012YQ120060);The Program of Introducing Talents of Discipline to Universities of China (111 Program);the Foundation of 100 Young Chongqing University (project 0903005203191) |
| Indexed By | SCI |
| If | 5.228 |
| Language | 英语 |
| compositor | 第二作者单位 |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.licp.cn/handle/362003/19064 |
| Collection | 羰基合成与选择氧化国家重点实验室（OSSO） |
| Corresponding Author | Lei AW(雷爱文) |
| Affiliation | 1.Wuhan Univ, Inst Adv Studies, Coll Chem & Mol Sci, Wuhan 430072, Hubei, Peoples R China 2.Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China 3.Chongqing Univ, Sch Chem & Chem Engn, Chongqing 400030, Peoples R China 4.Wuhan Univ, Coll Chem & Mol Sci, Wuhan 430072, Hubei, Peoples R China |
| Recommended Citation GB/T 7714 | Zhou, Liangliang,Yi, Hong,Zhu, Lei,et al. Tuning the Reactivity of Radical through a Triplet Diradical Cu(II) Intermediate in Radical Oxidative Cross-Coupling[J]. Scientific Reports,2015,5:15934(1-12). |
| APA | Zhou, Liangliang.,Yi, Hong.,Zhu, Lei.,Qi, Xiaotian.,Jiang, Hanpeng.,...&雷爱文.(2015).Tuning the Reactivity of Radical through a Triplet Diradical Cu(II) Intermediate in Radical Oxidative Cross-Coupling.Scientific Reports,5,15934(1-12). |
| MLA | Zhou, Liangliang,et al."Tuning the Reactivity of Radical through a Triplet Diradical Cu(II) Intermediate in Radical Oxidative Cross-Coupling".Scientific Reports 5(2015):15934(1-12). |
| Files in This Item: | ||||||
| File Name/Size | DocType | Version | Access | License | ||
| srep15934.pdf（2068KB） | 期刊论文 | 作者接受稿 | 开放获取 | CC BY-NC-SA | View Application Full Text | |
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