The Mechanism of NO Bond Cleavage in Rhodium-Catalyzed CH Bond Functionalization of Quinoline N-oxides with Alkynes: A Computational Study
文献类型：期刊论文
| 作者 | Li, Yingzi1; Liu, Song1; Qi, Zisong2; Qi, Xiaotian1; Li, Xingwei2; Lan, Yu1 |
| 刊名 | chemistry-a european journal
 |
| 出版日期 | 2015-07-06 |
| 卷号 | 21期号:28页码:10131-10137 |
| 关键词 | CH bond activation cleavage reactions density function calculations quinolines rhodium |
| 英文摘要 | metal-catalyzed ch activation not only offers important strategies to construct new bonds, it also allows the merge of important research areas. when quinoline n-oxide is used as an arene source in ch activation studies, the no bond can act as a directing group as well as an o-atom donor. the newly reported density functional theory method, m11l, has been used to elucidate the mechanistic details of the coupling between quinoline no bond and alkynes, which results in ch activation and o-atom transfer. the computational results indicated that the most favorable pathway involves an electrophilic deprotonation, an insertion of an acetylene group into a rhc bond, a reductive elimination to form an oxazinoquinolinium-coordinated rh-i intermediate, an oxidative addition to break the no bond, and a protonation reaction to regenerate the active catalyst. the regioselectivity of the reaction has also been studied by using prop-1-yn-1-ylbenzene as a model unsymmetrical substrate. theoretical calculations suggested that 1-phenyl-2-quinolinylpropanone would be the major product because of better conjugation between the phenyl group and enolate moiety in the corresponding transition state of the regioselectivity-determining step. these calculated data are consistent with the experimental observations. |
| WOS标题词 | science & technology ; physical sciences |
| 类目[WOS] | chemistry, multidisciplinary |
| 研究领域[WOS] | chemistry |
| 关键词[WOS] | direct ortho arylation ; oxidizing directing group ; h activation ; c-8 position ; organozinc reagents ; organic-synthesis ; aromatic ketones ; room-temperature ; carbon-hydrogen ; boronic acids |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS记录号 | WOS:000357026700025 |
| 公开日期 | 2016-05-09 |
| 源URL | [http://cas-ir.dicp.ac.cn/handle/321008/146387]  |
| 专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
| 作者单位 | 1.Chongqing Univ, Sch Chem & Chem Engn, Chongqing 400030, Peoples R China 2.Chinese Acad Sci, Dalian Inst Chem Phys, Dalian 116023, Peoples R China |
| 推荐引用方式 GB/T 7714 | Li, Yingzi,Liu, Song,Qi, Zisong,et al. The Mechanism of NO Bond Cleavage in Rhodium-Catalyzed CH Bond Functionalization of Quinoline N-oxides with Alkynes: A Computational Study[J]. chemistry-a european journal,2015,21(28):10131-10137. |
| APA | Li, Yingzi,Liu, Song,Qi, Zisong,Qi, Xiaotian,Li, Xingwei,&Lan, Yu.(2015).The Mechanism of NO Bond Cleavage in Rhodium-Catalyzed CH Bond Functionalization of Quinoline N-oxides with Alkynes: A Computational Study.chemistry-a european journal,21(28),10131-10137. |
| MLA | Li, Yingzi,et al."The Mechanism of NO Bond Cleavage in Rhodium-Catalyzed CH Bond Functionalization of Quinoline N-oxides with Alkynes: A Computational Study".chemistry-a european journal 21.28(2015):10131-10137. |
入库方式： OAI收割
来源：大连化学物理研究所
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