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Filimonov VO, Dianova LN, Galata KA, et al. Switchable Synthesis of 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles from 2-Cyanothioacetamides under Diazo Group Transfer Conditions. J Org Chem. 2017;82(8):4056-4071doi: 10.1021/acs.joc.6b02736.
Filimonov, V. O., Dianova, L. N., Galata, K. A., Beryozkina, T. V., Novikov, M. S., Berseneva, V. S., Eltsov, O. S., Lebedev, A. T., Slepukhin, P. A., & Bakulev, V. A. (2017). Switchable Synthesis of 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles from 2-Cyanothioacetamides under Diazo Group Transfer Conditions. The Journal of organic chemistry, 82(8), 4056-4071. https://doi.org/10.1021/acs.joc.6b02736
Filimonov, Valeriy O, et al. "Switchable Synthesis of 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles from 2-Cyanothioacetamides under Diazo Group Transfer Conditions." The Journal of organic chemistry vol. 82,8 (2017): 4056-4071. doi: https://doi.org/10.1021/acs.joc.6b02736
Filimonov VO, Dianova LN, Galata KA, Beryozkina TV, Novikov MS, Berseneva VS, Eltsov OS, Lebedev AT, Slepukhin PA, Bakulev VA. Switchable Synthesis of 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles from 2-Cyanothioacetamides under Diazo Group Transfer Conditions. J Org Chem. 2017 Apr 21;82(8):4056-4071. doi: 10.1021/acs.joc.6b02736. Epub 2017 Apr 03. PMID: 28328204.
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J Org Chem. 2017 Apr 21;82(8):4056-4071. doi: 10.1021/acs.joc.6b02736. Epub 2017 Apr 03.

Switchable Synthesis of 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles from 2-Cyanothioacetamides under Diazo Group Transfer Conditions.

The Journal of organic chemistry

Valeriy O Filimonov, Lidia N Dianova, Kristina A Galata, Tetyana V Beryozkina, Mikhail S Novikov, Vera S Berseneva, Oleg S Eltsov, Albert T Lebedev, Pavel A Slepukhin, Vasiliy A Bakulev

Affiliations

  1. Ural Federal University named after the first President of Russia B. N. Yeltsin , 19 Mira st., Yekaterinburg 620002, Russia.
  2. Institute of Chemistry, St. Petersburg State University , 7/9 Universitetskaya nab., St. Petersburg 199034, Russia.
  3. Department of Chemistry, Lomonosov Moscow State University , Moscow 119991, Russia.
  4. I. Ya. Postovsky Institute of Organic Synthesis, Ural Branch of Russian Academy of Sciences , 20 S. Kovalevskaya st., Yekaterinburg 620990, Russia.

PMID: 28328204 DOI: 10.1021/acs.joc.6b02736

Abstract

High yield solvent-base-controlled, transition metal-free synthesis of 4,5-functionalized 1,2,3-thiadiazoles and 1,2,3-triazoles from 2-cyanothioacetamides and sulfonyl azides is described. Under diazo transfer conditions in the presence of a base in an aprotic solvent 2-cyanothioacetamides operating as C-C-S building blocks produce 5-amino-4-cyano-1,2,3-thiadiazoles exclusively. The use of alkoxide/alcohol system completely switches the reaction course due to the change of one of the reaction centers in the 2-cyanothioacetamide (C-C-N building block) resulting in the formation of 5-sulfonamido-1,2,3-triazole-4-carbothioamide sodium salts as the only products. The latter serve as good precursors for 5-amino-1,2,3-thiadiazole-4-carboximidamides, the products of Cornforth-type rearrangement occurring in neutral protic medium or under acid conditions. According to DFT calculations (B3LYP/6-311+G(d,p)) the rearrangement proceeds via intermediate formation of a diazo compound, and can be catalyzed by acids via the protonation of oxygen atom of the sulfonamide group.

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