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Title: Selective Synthesis of Azoloyl NH-1,2,3-Triazoles and Azolyl Diazoketones: Experimental and Computational Insights
Authors: Shafran, Y. M.
Hussein, A. A.
Beliaev, N. A.
Shevyrin, V. A.
Shityakov, S.
Beryozkina, T. V.
Bakulev, V. A.
Issue Date: 2022
Publisher: American Chemical Society
American Chemical Society (ACS)
Citation: Selective Synthesis of Azoloyl NH-1,2,3-Triazoles and Azolyl Diazoketones: Experimental and Computational Insights / Y. M. Shafran, A. A. Hussein, N. A. Beliaev et al. — DOI 10.3847/PSJ/aba7c2 // ACS Omega. — 2022. — Vol. 7. — Iss. 6. — P. 5008-5031.
Abstract: Here, we report that the reaction of enaminones, from a class of azole series, with sulfonyl azides leads to a difficult-to-separate mixture of two pairs of compounds: (1) 4-azoloyl-NH-1,2,3-triazoles with sulfonamides and (2) azolyl diazoketones with N-sulfonamidines, as a result of the implementation of two competing reactions. On one hand, the electron-donating methyl or methoxy group in the aryl para-position of arylsulfonyl azides favors the production of NH-1,2,3-triazoles together with sulfonamides. On the other hand, the use of highly electrophilic 4-nitrophenylsulfonyl azide promotes the formation of diazoketones and sulfonamidines. It is shown that the direction of each reaction is not only controlled by the nature of the initial enaminones and sulfonyl azides but also depends on the tested solvent. The problem of removing sulfonamides and amidines from the desired products was solved for the first time using new water-soluble enaminones. Based on the experimental and computational studies, the factors contributing to the selective course of alternative reactions were identified, and methods for the synthesis of azoloyl-NH-1,2,3-triazoles and azolyl diazoketones were developed. Density functional theory (DFT) results have shown that the 1,3-dipolar cycloaddition is totally driven toward one single regioisomer with a high asynchronous bond formation, and the introduction of an electron-deficient group in sulfonyl azides induces faster cycloaddition. Additionally, DFT calculations were used to gain further mechanistic insights on the reaction studied here. © 2022 American Chemical Society. All rights reserved.
Access: info:eu-repo/semantics/openAccess
SCOPUS ID: 85124601021
WOS ID: 000757894800001
PURE ID: 29726992
ISSN: 2470-1343
DOI: 10.3847/PSJ/aba7c2
metadata.dc.description.sponsorship: This work was supported by the Russian Science Foundation (grant no. 18-13-00161, prolongation). A.A.H. thanks the computational resources accessed via Iridis4 provided by the University of Southampton.
RSCF project card: 18-13-00161
Appears in Collections:Научные публикации, проиндексированные в SCOPUS и WoS CC

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