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The Mechanism of N-O Bond Cleavage in Rhodium-Catalyzed C-H Bond Functionalization of Quinoline N-oxides with Alkynes: A Computational Study.
Chemistry. 2015 Jul 06; 21(28):10131-7.C

Abstract

Metal-catalyzed C-H 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 C-H activation studies, the N-O 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 N-O bond and alkynes, which results in C-H 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 Rh-C bond, a reductive elimination to form an oxazinoquinolinium-coordinated Rh(I) intermediate, an oxidative addition to break the N-O 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.

Authors+Show Affiliations

School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030 (China).School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030 (China).Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China).School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030 (China).Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China). xwli@dicp.ac.cn.School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030 (China). lanyu@cqu.edu.cn.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

26059235

Citation

Li, Yingzi, et al. "The Mechanism of N-O Bond Cleavage in Rhodium-Catalyzed C-H Bond Functionalization of Quinoline N-oxides With Alkynes: a Computational Study." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 21, no. 28, 2015, pp. 10131-7.
Li Y, Liu S, Qi Z, et al. The Mechanism of N-O Bond Cleavage in Rhodium-Catalyzed C-H Bond Functionalization of Quinoline N-oxides with Alkynes: A Computational Study. Chemistry. 2015;21(28):10131-7.
Li, Y., Liu, S., Qi, Z., Qi, X., Li, X., & Lan, Y. (2015). The Mechanism of N-O Bond Cleavage in Rhodium-Catalyzed C-H Bond Functionalization of Quinoline N-oxides with Alkynes: A Computational Study. Chemistry (Weinheim an Der Bergstrasse, Germany), 21(28), 10131-7. https://doi.org/10.1002/chem.201500290
Li Y, et al. The Mechanism of N-O Bond Cleavage in Rhodium-Catalyzed C-H Bond Functionalization of Quinoline N-oxides With Alkynes: a Computational Study. Chemistry. 2015 Jul 6;21(28):10131-7. PubMed PMID: 26059235.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - The Mechanism of N-O Bond Cleavage in Rhodium-Catalyzed C-H Bond Functionalization of Quinoline N-oxides with Alkynes: A Computational Study. AU - Li,Yingzi, AU - Liu,Song, AU - Qi,Zisong, AU - Qi,Xiaotian, AU - Li,Xingwei, AU - Lan,Yu, Y1 - 2015/06/08/ PY - 2015/01/22/received PY - 2015/6/11/entrez PY - 2015/6/11/pubmed PY - 2015/6/11/medline KW - CH bond activation KW - cleavage reactions KW - density function calculations KW - quinolines KW - rhodium SP - 10131 EP - 7 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 21 IS - 28 N2 - Metal-catalyzed C-H 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 C-H activation studies, the N-O 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 N-O bond and alkynes, which results in C-H 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 Rh-C bond, a reductive elimination to form an oxazinoquinolinium-coordinated Rh(I) intermediate, an oxidative addition to break the N-O 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. SN - 1521-3765 UR - https://www.unboundmedicine.com/medline/citation/26059235/The_Mechanism_of_N_O_Bond_Cleavage_in_Rhodium_Catalyzed_C_H_Bond_Functionalization_of_Quinoline_N_oxides_with_Alkynes:_A_Computational_Study_ L2 - https://doi.org/10.1002/chem.201500290 DB - PRIME DP - Unbound Medicine ER -
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