Substrate-Dependent Two-State Reactivity in Iron-Catalyzed Alkene [2+2] Cycloaddition Reactions
文献类型：期刊论文
| 作者 | Hu, Lianrui1,2; Chen, Hui1 |
| 刊名 | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
 |
| 出版日期 | 2017-11-08 |
| 卷号 | 139期号:44页码:15564-15567 |
| 英文摘要 | Iron-catalyzed alkene [2+2] cycloaddition reactions represent a promising stepwise pathway to effect the kinetically hindered concerted [2+2] cycloaddition. However, the fundamental reactivity paradigm of these reactions remains unclear. Based on high level combined CASPT2/DFT modelings, herein we reveal an unprecedented substrate-dependent two-state reactivity scenario for the key C-C coupling in this iron catalysis, in which the representative substrates of mono-olefins only and mono-olefin plus 1,3-diene exhibit different reactivity paradigms. The role of the redox-active ligand is found to generate a ferric oxidation state for the metallacyclic intermediate of C-C coupling, thereby rendering a thermodynamically more accessible Fem/Fei reductive elimination process compared with the otherwise Fe-II/ Fe-0 one. The enhancement of the spin state transition efficiency between the singlet and triplet states is predicted as an alternative way to increase the C-C coupling reactivity in the cross [2+2] cycloaddition reactions between mono-olefins and dienes. This work highlights the ab initio multi-reference 'method in describing 'very complicated open-shell iron catalysis.. |
| 语种 | 英语 |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/39137]  |
| 专题 | 化学研究所_光化学实验室 |
| 作者单位 | 1.Chinese Acad Sci, Inst Chem, CAS Res Educ Ctr Excellence Mol Sci, CAS Key Lab Photochem,BNLMS, Beijing 100190, Peoples R China 2.Univ Chinese Acad Sci, Beijing 100049, Peoples R China |
| 推荐引用方式 GB/T 7714 | Hu, Lianrui,Chen, Hui. Substrate-Dependent Two-State Reactivity in Iron-Catalyzed Alkene [2+2] Cycloaddition Reactions[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2017,139(44):15564-15567. |
| APA | Hu, Lianrui,&Chen, Hui.(2017).Substrate-Dependent Two-State Reactivity in Iron-Catalyzed Alkene [2+2] Cycloaddition Reactions.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,139(44),15564-15567. |
| MLA | Hu, Lianrui,et al."Substrate-Dependent Two-State Reactivity in Iron-Catalyzed Alkene [2+2] Cycloaddition Reactions".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 139.44(2017):15564-15567. |
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来源：化学研究所
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