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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
KeywordCh Bond Activation Cleavage Reactions Density Function Calculations Quinolines Rhodium
Source PublicationCHEMISTRY-A EUROPEAN JOURNAL
2015-07-06
DOI10.1002/chem.201500290
Volume21Issue:28Pages:10131-10137
Indexed BySCI
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences
WOS SubjectChemistry, Multidisciplinary
WOS Research AreaChemistry
WOS KeywordDIRECT ORTHO ARYLATION ; OXIDIZING DIRECTING GROUP ; H ACTIVATION ; C-8 POSITION ; ORGANOZINC REAGENTS ; ORGANIC-SYNTHESIS ; AROMATIC KETONES ; ROOM-TEMPERATURE ; CARBON-HYDROGEN ; BORONIC ACIDS
AbstractMetal-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.
Language英语
WOS IDWOS:000357026700025
Citation statistics
Cited Times:41[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/146387
Collection中国科学院大连化学物理研究所
Affiliation1.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
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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