Controlling Pd-Catalyzed N-Arylation and Dimroth Rearrangement in the Synthesis of N,1-Diaryl-1H-tetrazol-5-amines
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2021
Authors
Nikolić, Andrea
Stanić, Jelena
Zlatar, Matija
Gruden, Maja

Anđelković, Boban D.

Selaković, Života

Ajdačić, Vladimir

Opsenica, Igor

Article (Published version)

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The Pd-catalyzed N-arylation method for the synthesis of eighteen N,1-diaryl-1H-tetrazol-5-amine derivatives is reported. By running the reactions at 35 °C, compounds were isolated as single isomers since the undesired Dimroth rearrangement was completely suppressed. Furthermore, the Dimroth rearrangement of N,1-diaryl-1H-tetrazol-5-amines was rationalized by conducting comprehensive experiments and NMR analysis as well as density functional theory (DFT) calculations of thermodynamic stability of the compounds. It was established that the Dimroth rearrangement is thermodynamically controlled, and the equilibrium of the reaction is determined by the stability of the corresponding isomers. The mechanism was investigated by additional DFT calculations, and the opening of the tetrazole ring was shown to be the rate-determining step. By maneuvering Pd-catalyzed N-arylation and the subsequent Dimroth rearrangement, two more N,1-diaryl-1H-tetrazol-5-amine derivatives were acquired, which othe...rwise cannot be synthesized by employing the C–N cross-coupling reaction.
Keywords:
Pd-catalyzed N-arylation / synthesis / tetrazoles / DFT / mechanism / Dimroth rearrangement / stability / NMR analysis / thermodynamical control / reactions / equilibrium / rate-determining step / isomersSource:
The Journal of Organic Chemistry, 2021, 86, 6, 4794-4803Publisher:
- American Chemical Society (ACS)
Funding / projects:
- Ministry of Education, Science and Technological Development, Republic of Serbia, Grant no. 200168 (University of Belgrade, Faculty of Chemistry) (RS-200168)
- Ministry of Education, Science and Technological Development, Republic of Serbia, Grant no. 200288 (Innovation Center of the Faculty of Chemistry) (RS-200288)
- Ministry of Education, Science and Technological Development, Republic of Serbia, Grant no. 200026 (University of Belgrade, Institute of Chemistry, Technology and Metallurgy - IChTM) (RS-200026)
- Serbian Academy of Sciences and Arts (01-2019-F65)
- Reinforcement of the Faculty of Chemistry, University of Belgrade, towards becoming a Center of Excellence in the region of WB for Molecular Biotechnology and Food research (EU-256716)
Note:
- The peer-reviewed version: https://cherry.chem.bg.ac.rs/handle/123456789/4359
- Supplementary data: https://cherry.chem.bg.ac.rs/handle/123456789/4360
Related info:
- Version of
https://cherry.chem.bg.ac.rs/handle/123456789/4359 - Referenced by
https://cherry.chem.bg.ac.rs/handle/123456789/4360
DOI: 10.1021/acs.joc.1c00282
ISSN: 0022-3263; 1520-6904
PubMed: 33683905
WoS: 000631442900036
Scopus: 2-s2.0-85103457952
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Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Nikolić, Andrea AU - Stanić, Jelena AU - Zlatar, Matija AU - Gruden, Maja AU - Anđelković, Boban D. AU - Selaković, Života AU - Ajdačić, Vladimir AU - Opsenica, Igor PY - 2021 UR - https://cherry.chem.bg.ac.rs/handle/123456789/4358 AB - The Pd-catalyzed N-arylation method for the synthesis of eighteen N,1-diaryl-1H-tetrazol-5-amine derivatives is reported. By running the reactions at 35 °C, compounds were isolated as single isomers since the undesired Dimroth rearrangement was completely suppressed. Furthermore, the Dimroth rearrangement of N,1-diaryl-1H-tetrazol-5-amines was rationalized by conducting comprehensive experiments and NMR analysis as well as density functional theory (DFT) calculations of thermodynamic stability of the compounds. It was established that the Dimroth rearrangement is thermodynamically controlled, and the equilibrium of the reaction is determined by the stability of the corresponding isomers. The mechanism was investigated by additional DFT calculations, and the opening of the tetrazole ring was shown to be the rate-determining step. By maneuvering Pd-catalyzed N-arylation and the subsequent Dimroth rearrangement, two more N,1-diaryl-1H-tetrazol-5-amine derivatives were acquired, which otherwise cannot be synthesized by employing the C–N cross-coupling reaction. PB - American Chemical Society (ACS) T2 - The Journal of Organic Chemistry T1 - Controlling Pd-Catalyzed N-Arylation and Dimroth Rearrangement in the Synthesis of N,1-Diaryl-1H-tetrazol-5-amines VL - 86 IS - 6 SP - 4794 EP - 4803 DO - 10.1021/acs.joc.1c00282 ER -
@article{ author = "Nikolić, Andrea and Stanić, Jelena and Zlatar, Matija and Gruden, Maja and Anđelković, Boban D. and Selaković, Života and Ajdačić, Vladimir and Opsenica, Igor", year = "2021", abstract = "The Pd-catalyzed N-arylation method for the synthesis of eighteen N,1-diaryl-1H-tetrazol-5-amine derivatives is reported. By running the reactions at 35 °C, compounds were isolated as single isomers since the undesired Dimroth rearrangement was completely suppressed. Furthermore, the Dimroth rearrangement of N,1-diaryl-1H-tetrazol-5-amines was rationalized by conducting comprehensive experiments and NMR analysis as well as density functional theory (DFT) calculations of thermodynamic stability of the compounds. It was established that the Dimroth rearrangement is thermodynamically controlled, and the equilibrium of the reaction is determined by the stability of the corresponding isomers. The mechanism was investigated by additional DFT calculations, and the opening of the tetrazole ring was shown to be the rate-determining step. By maneuvering Pd-catalyzed N-arylation and the subsequent Dimroth rearrangement, two more N,1-diaryl-1H-tetrazol-5-amine derivatives were acquired, which otherwise cannot be synthesized by employing the C–N cross-coupling reaction.", publisher = "American Chemical Society (ACS)", journal = "The Journal of Organic Chemistry", title = "Controlling Pd-Catalyzed N-Arylation and Dimroth Rearrangement in the Synthesis of N,1-Diaryl-1H-tetrazol-5-amines", volume = "86", number = "6", pages = "4794-4803", doi = "10.1021/acs.joc.1c00282" }
Nikolić, A., Stanić, J., Zlatar, M., Gruden, M., Anđelković, B. D., Selaković, Ž., Ajdačić, V.,& Opsenica, I.. (2021). Controlling Pd-Catalyzed N-Arylation and Dimroth Rearrangement in the Synthesis of N,1-Diaryl-1H-tetrazol-5-amines. in The Journal of Organic Chemistry American Chemical Society (ACS)., 86(6), 4794-4803. https://doi.org/10.1021/acs.joc.1c00282
Nikolić A, Stanić J, Zlatar M, Gruden M, Anđelković BD, Selaković Ž, Ajdačić V, Opsenica I. Controlling Pd-Catalyzed N-Arylation and Dimroth Rearrangement in the Synthesis of N,1-Diaryl-1H-tetrazol-5-amines. in The Journal of Organic Chemistry. 2021;86(6):4794-4803. doi:10.1021/acs.joc.1c00282 .
Nikolić, Andrea, Stanić, Jelena, Zlatar, Matija, Gruden, Maja, Anđelković, Boban D., Selaković, Života, Ajdačić, Vladimir, Opsenica, Igor, "Controlling Pd-Catalyzed N-Arylation and Dimroth Rearrangement in the Synthesis of N,1-Diaryl-1H-tetrazol-5-amines" in The Journal of Organic Chemistry, 86, no. 6 (2021):4794-4803, https://doi.org/10.1021/acs.joc.1c00282 . .