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Mechanistic Investigations of the AuCl3-Catalyzed Nitrene Insertion into an Aromatic C-H Bond of Mesitylene.
J Org Chem. 2015 Jun 05; 80(11):5795-803.JO

Abstract

The AuCl3-catalyzed nitrene insertion into an aromatic C-H bond of mesitylene demonstrates a unique activity and chemoselectivity in direct C-H aminations. Mechanisms for catalytic nitrene insertion are examined here using theory. The AuCl3 catalyst favors formation of a complex with the PhI═NNs (Ns = p-nitrobenzenesulfonyl) substrate, followed by the appearance of the key (N-chloro-4-nitrophenylsulfonamido)gold(III) chloride intermediate (INT5). However, the putative gold(III)-nitrene analogue (AuCl3-NNs complex) is thermodynamically unfavorable compared with INT5. Therefore, INT5 is suggested to play a critical role in the AuCl3-promoted aromatic C-H bond amination, a prediction in contrast to the previously reported crucial metal-nitrene intermediates. The activation of a C(sp(2))-H bond of mesitylene via σ-bond metathesis is proposed based on INT5, and the subsequent detailed pathways for the aromatic C-H bond amination are computationally explored. A chemoselective nitrene insertion into a mesitylene aromatic C-H bond, instead of a benzylic C-H bond, is rationalized for the AuCl3-catalyzed amination.

Authors+Show Affiliations

†College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou Industrial Park, Suzhou, Jiangsu 215123, China.†College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou Industrial Park, Suzhou, Jiangsu 215123, China.†College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou Industrial Park, Suzhou, Jiangsu 215123, China.†College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou Industrial Park, Suzhou, Jiangsu 215123, China.‡Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602, United States.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

26014208

Citation

Hou, Kaipeng, et al. "Mechanistic Investigations of the AuCl3-Catalyzed Nitrene Insertion Into an Aromatic C-H Bond of Mesitylene." The Journal of Organic Chemistry, vol. 80, no. 11, 2015, pp. 5795-803.
Hou K, Qi M, Liu J, et al. Mechanistic Investigations of the AuCl3-Catalyzed Nitrene Insertion into an Aromatic C-H Bond of Mesitylene. J Org Chem. 2015;80(11):5795-803.
Hou, K., Qi, M., Liu, J., Bao, X., & Schaefer, H. F. (2015). Mechanistic Investigations of the AuCl3-Catalyzed Nitrene Insertion into an Aromatic C-H Bond of Mesitylene. The Journal of Organic Chemistry, 80(11), 5795-803. https://doi.org/10.1021/acs.joc.5b00764
Hou K, et al. Mechanistic Investigations of the AuCl3-Catalyzed Nitrene Insertion Into an Aromatic C-H Bond of Mesitylene. J Org Chem. 2015 Jun 5;80(11):5795-803. PubMed PMID: 26014208.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Mechanistic Investigations of the AuCl3-Catalyzed Nitrene Insertion into an Aromatic C-H Bond of Mesitylene. AU - Hou,Kaipeng, AU - Qi,Miao, AU - Liu,Jiajun, AU - Bao,Xiaoguang, AU - Schaefer,Henry F,3rd Y1 - 2015/05/27/ PY - 2015/5/28/entrez PY - 2015/5/28/pubmed PY - 2015/5/28/medline SP - 5795 EP - 803 JF - The Journal of organic chemistry JO - J Org Chem VL - 80 IS - 11 N2 - The AuCl3-catalyzed nitrene insertion into an aromatic C-H bond of mesitylene demonstrates a unique activity and chemoselectivity in direct C-H aminations. Mechanisms for catalytic nitrene insertion are examined here using theory. The AuCl3 catalyst favors formation of a complex with the PhI═NNs (Ns = p-nitrobenzenesulfonyl) substrate, followed by the appearance of the key (N-chloro-4-nitrophenylsulfonamido)gold(III) chloride intermediate (INT5). However, the putative gold(III)-nitrene analogue (AuCl3-NNs complex) is thermodynamically unfavorable compared with INT5. Therefore, INT5 is suggested to play a critical role in the AuCl3-promoted aromatic C-H bond amination, a prediction in contrast to the previously reported crucial metal-nitrene intermediates. The activation of a C(sp(2))-H bond of mesitylene via σ-bond metathesis is proposed based on INT5, and the subsequent detailed pathways for the aromatic C-H bond amination are computationally explored. A chemoselective nitrene insertion into a mesitylene aromatic C-H bond, instead of a benzylic C-H bond, is rationalized for the AuCl3-catalyzed amination. SN - 1520-6904 UR - https://www.unboundmedicine.com/medline/citation/26014208/Mechanistic_Investigations_of_the_AuCl3_Catalyzed_Nitrene_Insertion_into_an_Aromatic_C_H_Bond_of_Mesitylene_ L2 - https://doi.org/10.1021/acs.joc.5b00764 DB - PRIME DP - Unbound Medicine ER -
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