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The Mechanism of NO Bond Cleavage in Rhodium-Catalyzed CH Bond Functionalization of Quinoline N-oxides with Alkynes: A Computational Study
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
2015-07-06
DOI10.1002/chem.201500290
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
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
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.
语种英语
WOS记录号WOS:000357026700025
引用统计
文献类型期刊论文
条目标识符http://cas-ir.dicp.ac.cn/handle/321008/146387
专题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
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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.
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