Controlling Pd-Catalyzed N-Arylation and Dimroth Rearrangement in the Synthesis of N,1-Diaryl-1H-tetrazol-5-amines
Autori
Nikolić, AndreaStanić, Jelena
Zlatar, Matija
Gruden, Maja
Anđelković, Boban
Selaković, Života
Ajdačić, Vladimir
Opsenica, Igor
Članak u časopisu (Recenzirana verzija)
Metapodaci
Prikaz svih podataka o dokumentuApstrakt
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.
Ključne reči:
Pd-catalyzed N-arylation / synthesis / tetrazoles / DFT / mechanism / Dimroth rearrangement / stability / NMR analysis / thermodynamical control / reactions / equilibrium / rate-determining step / isomersIzvor:
The Journal of Organic Chemistry, 2021, 86, 6, 4794-4803Izdavač:
- American Chemical Society (ACS)
Finansiranje / projekti:
- Ministarstvo nauke, tehnološkog razvoja i inovacija Republike Srbije, institucionalno finansiranje - 200168 (Univerzitet u Beogradu, Hemijski fakultet) (RS-MESTD-inst-2020-200168)
- Ministarstvo nauke, tehnološkog razvoja i inovacija Republike Srbije, institucionalno finansiranje - 200288 (Inovacioni centar Hemijskog fakulteta u Beogradu doo) (RS-MESTD-inst-2020-200288)
- Ministarstvo nauke, tehnološkog razvoja i inovacija Republike Srbije, institucionalno finansiranje - 200026 (Univerzitet u Beogradu, Institut za hemiju, tehnologiju i metalurgiju - IHTM) (RS-MESTD-inst-2020-200026)
- 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-FP7-256716)
Napomena:
- This is the peer-reviewed, authors’ version of the article: Nikolić, A., Stanić, J., Zlatar, M., Gruden, M., Anđelković, B., 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. The Journal of Organic Chemistry, American Chemical Society (ACS)., 86(6), 4794-4803. https://doi.org/10.1021/acs.joc.1c00282
- This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Organic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.joc.1c00282
- The published version: https://cer.ihtm.bg.ac.rs/handle/123456789/4431
- The supporting information: https://cer.ihtm.bg.ac.rs/handle/123456789/4444
Povezane informacije:
- Druga verzija
https://doi.org/10.1021/acs.joc.1c00282 - Druga verzija
https://cer.ihtm.bg.ac.rs/handle/123456789/4431 - Povezani sadržaj
https://cer.ihtm.bg.ac.rs/handle/123456789/4444
DOI: 10.1021/acs.joc.1c00282
ISSN: 0022-3263; 1520-6904
PubMed: 33683905
WoS: 000631442900036
Scopus: 2-s2.0-85103457952
Institucija/grupa
IHTMTY - JOUR AU - Nikolić, Andrea AU - Stanić, Jelena AU - Zlatar, Matija AU - Gruden, Maja AU - Anđelković, Boban AU - Selaković, Života AU - Ajdačić, Vladimir AU - Opsenica, Igor PY - 2021 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/4443 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 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., 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 B, 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, 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 . .