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题名: The Mechanism of NO Bond Cleavage in Rhodium-Catalyzed CH Bond Functionalization of Quinoline N-oxides with Alkynes: A Computational Study
作者: Li, Yingzi1;  Liu, Song1;  Qi, Zisong2;  Qi, Xiaotian1;  Li, Xingwei2;  Lan, Yu1
关键词: CH bond activation ;  cleavage reactions ;  density function calculations ;  quinolines ;  rhodium
刊名: CHEMISTRY-A EUROPEAN JOURNAL
发表日期: 2015-07-06
DOI: 10.1002/chem.201500290
卷: 21, 期:28, 页:10131-10137
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Multidisciplinary
研究领域[WOS]: Chemistry
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.
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
语种: 英语
WOS记录号: WOS:000357026700025
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/146387
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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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

Recommended Citation:
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.
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