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Acid-Catalyzed Rearrangements of 3-Aryloxirane-2-Carboxamides: Novel DFT Mechanistic Insights.
ChemistryOpen. 2020 Jul; 9(7):743-747.C

Abstract

Efficient synthesis of 3-arylquinolin-2(1H)-ones and N-(2-carboxyaryl)-oxalamides from protic acid-catalyzed rearrangements of 3-aryloxirane-2-carboxamides was achieved recently but not well understood. In contrast to the classical Meinwald rearrangement, extensive DFT calculations reveal that the proximal aryl and amide groups have strong synergetic effects to control the amide-aided and aryl-directed oxirane-opening and further rearrangement sequences. The ortho-nitro substituent of the proximal aryl is directly involved in a nucleophilic oxirane ring-opening, the amide C=O is an important proton shuttle for facile H-shifts, while the N-aryl may act as a potential ring-closing site via Friedel-Crafts alkylation. The mechanistic insights are useful for rational design of novel synthesis by changing the aryl and amide functional groups proximal to the oxirane ring.

Authors+Show Affiliations

Mulliken Center for Theoretical Chemistry University of Bonn Beringstr. 4 53115 Bonn Germany.Mulliken Center for Theoretical Chemistry University of Bonn Beringstr. 4 53115 Bonn Germany.Arbuzov Institute of Organic and Physical Chemistry FRC Kazan Scientific Center of RAS Arbuzov Str. 8 420088 Kazan Russia.Arbuzov Institute of Organic and Physical Chemistry FRC Kazan Scientific Center of RAS Arbuzov Str. 8 420088 Kazan Russia.Arbuzov Institute of Organic and Physical Chemistry FRC Kazan Scientific Center of RAS Arbuzov Str. 8 420088 Kazan Russia.Mulliken Center for Theoretical Chemistry University of Bonn Beringstr. 4 53115 Bonn Germany.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

32626644

Citation

Qu, Zheng-Wang, et al. "Acid-Catalyzed Rearrangements of 3-Aryloxirane-2-Carboxamides: Novel DFT Mechanistic Insights." ChemistryOpen, vol. 9, no. 7, 2020, pp. 743-747.
Qu ZW, Zhu H, Katsyuba SA, et al. Acid-Catalyzed Rearrangements of 3-Aryloxirane-2-Carboxamides: Novel DFT Mechanistic Insights. ChemistryOpen. 2020;9(7):743-747.
Qu, Z. W., Zhu, H., Katsyuba, S. A., Mamedova, V. L., Mamedov, V. A., & Grimme, S. (2020). Acid-Catalyzed Rearrangements of 3-Aryloxirane-2-Carboxamides: Novel DFT Mechanistic Insights. ChemistryOpen, 9(7), 743-747. https://doi.org/10.1002/open.202000110
Qu ZW, et al. Acid-Catalyzed Rearrangements of 3-Aryloxirane-2-Carboxamides: Novel DFT Mechanistic Insights. ChemistryOpen. 2020;9(7):743-747. PubMed PMID: 32626644.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Acid-Catalyzed Rearrangements of 3-Aryloxirane-2-Carboxamides: Novel DFT Mechanistic Insights. AU - Qu,Zheng-Wang, AU - Zhu,Hui, AU - Katsyuba,Sergey A, AU - Mamedova,Vera L, AU - Mamedov,Vakhid A, AU - Grimme,Stefan, Y1 - 2020/07/01/ PY - 2020/04/21/received PY - 2020/05/20/revised PY - 2020/7/7/entrez PY - 2020/7/7/pubmed PY - 2020/7/7/medline KW - DFT calculations KW - acid catalysis KW - oxirane opening KW - reaction mechanism KW - synergetic effects SP - 743 EP - 747 JF - ChemistryOpen JO - ChemistryOpen VL - 9 IS - 7 N2 - Efficient synthesis of 3-arylquinolin-2(1H)-ones and N-(2-carboxyaryl)-oxalamides from protic acid-catalyzed rearrangements of 3-aryloxirane-2-carboxamides was achieved recently but not well understood. In contrast to the classical Meinwald rearrangement, extensive DFT calculations reveal that the proximal aryl and amide groups have strong synergetic effects to control the amide-aided and aryl-directed oxirane-opening and further rearrangement sequences. The ortho-nitro substituent of the proximal aryl is directly involved in a nucleophilic oxirane ring-opening, the amide C=O is an important proton shuttle for facile H-shifts, while the N-aryl may act as a potential ring-closing site via Friedel-Crafts alkylation. The mechanistic insights are useful for rational design of novel synthesis by changing the aryl and amide functional groups proximal to the oxirane ring. SN - 2191-1363 UR - https://www.unboundmedicine.com/medline/citation/32626644/Acid-Catalyzed_Rearrangements_of_3-Aryloxirane-2-Carboxamides:_Novel_DFT_Mechanistic_Insights L2 - https://doi.org/10.1002/open.202000110 DB - PRIME DP - Unbound Medicine ER -
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