pi-pi Interaction Assisted Hydrodefluorination of Perfluoroarenes by Gold Hydride: A Case of Synergistic Effect on C-F Bond Activation
文献类型：期刊论文
| 作者 | Lv, Hongbin; Zhan, Jin-Hui; Cai, Yuan-Bo; Yu, Yi; Wang, Bingwu; Zhang, Jun-Long |
| 刊名 | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
 |
| 出版日期 | 2012-10-03 |
| 卷号 | 134期号:39页码:16216-16227 |
| ISSN号 | 0002-7863 |
| DOI | 10.1021/ja305204y |
| 英文摘要 | "Synergistic effect" is prevalent in natural metalloenzymes in activating small molecules, and the success has inspired the development of artificial catalysts capable of unprecedented organic transformations. In this work, we found that the attractive pi-pi interaction between organic additives (as electron-donors) and the perfluorinated arenes (as electron acceptors) is effective in gold hydride catalyzed activation of C-F bonds, specifically hydrodefluorination (HDF) of perfluoroarenes catalyzed by the Sadighi's gold hydrides [(NHC)AuH] (NHC = N-heterocyclic carbene). Although a weak interaction between [(NHC)AuH] and perfluoroarenes was observed from H-1 NMR and UV-vis spectroscopies, low reactivity of [(NHC)AuH] toward HDF was found. In contrast, in the presence of p-N,N-dimethylaminopyridine (DMAP), the HDF of perfluoroarenes with silanes can be efficiently catalyzed by [(NHC)AuH], resulting in mainly the para-hydrodefluorinated products with up to 90% yield and 9 turnovers. The yield of the reaction increases with the more electron-withdrawing groups and degree of fluorination on the arenes, and the HDF reaction also tolerates different function groups (such as formyl, alkynyl, ketone, ester, and carboxylate groups), without reduction or hydrogenation of these function groups. To reveal the role of DMAP in the reactions, the possible pi-pi interaction between DMAP and perfluoroarenes was suggested by UV-vis spectral titrations, H-1 NMR spectroscopic studies, and DFT calculations. Moreover, H-1 and F-19-NMR studies show that this pi-pi interaction promotes hydrogen transfer from [(NHC)AuH] to pyridyl N atom, resulting in C-F bond cleavage. The interpretation of pi-pi interaction assisted C F activation is supported by the reduced activation barriers in the presence of DMAP (31.6 kcal/mol) than that in the absence of DMAP (40.8 kcal/mol) for this reaction. An analysis of the charge distribution and transition state geometries indicate that this HDF process is controlled by the pi-pi interaction between DMAP and perfluoroarenes, accompanied with the changes of partial atomic charges. |
| 语种 | 英语 |
| WOS记录号 | WOS:000309335000026 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/48433]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Zhang, Jun-Long |
| 作者单位 | Peking Univ, Beijing Natl Lab Mol Sci, State Key Lab Rare Earth Mat Chem & Applicat, Coll Chem & Mol Engn, Beijing 100871, Peoples R China |
| 推荐引用方式 GB/T 7714 | Lv, Hongbin,Zhan, Jin-Hui,Cai, Yuan-Bo,et al. pi-pi Interaction Assisted Hydrodefluorination of Perfluoroarenes by Gold Hydride: A Case of Synergistic Effect on C-F Bond Activation[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2012,134(39):16216-16227. |
| APA | Lv, Hongbin,Zhan, Jin-Hui,Cai, Yuan-Bo,Yu, Yi,Wang, Bingwu,&Zhang, Jun-Long.(2012).pi-pi Interaction Assisted Hydrodefluorination of Perfluoroarenes by Gold Hydride: A Case of Synergistic Effect on C-F Bond Activation.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,134(39),16216-16227. |
| MLA | Lv, Hongbin,et al."pi-pi Interaction Assisted Hydrodefluorination of Perfluoroarenes by Gold Hydride: A Case of Synergistic Effect on C-F Bond Activation".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 134.39(2012):16216-16227. |
入库方式： OAI收割
来源：化学研究所
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