volume 82 issue 8 pages 4056-4071

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

Lidia N Dianova 1
Kristina A Galata 1
Vera S Berseneva 1
Oleg S Eltsov 1
Publication typeJournal Article
Publication date2017-04-03
scimago Q2
wos Q1
SJR0.737
CiteScore6.1
Impact factor3.6
ISSN00223263, 15206904
Organic Chemistry
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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GOST |
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GOST Copy
Filimonov V. 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 // Journal of Organic Chemistry. 2017. Vol. 82. No. 8. pp. 4056-4071.
GOST all authors (up to 50) Copy
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. Switchable Synthesis of 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles from 2-Cyanothioacetamides under Diazo Group Transfer Conditions // Journal of Organic Chemistry. 2017. Vol. 82. No. 8. pp. 4056-4071.
RIS |
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RIS Copy
TY - JOUR
DO - 10.1021/acs.joc.6b02736
UR - https://pubs.acs.org/doi/10.1021/acs.joc.6b02736
TI - Switchable Synthesis of 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles from 2-Cyanothioacetamides under Diazo Group Transfer Conditions
T2 - Journal of Organic Chemistry
AU - Filimonov, Valeriy O
AU - Dianova, Lidia N
AU - Galata, Kristina A
AU - Beryozkina, Tetyana V
AU - Novikov, Mikhail S.
AU - Berseneva, Vera S
AU - Eltsov, Oleg S
AU - Lebedev, Albert T.
AU - Slepukhin, Pavel A.
AU - Bakulev, Vasiliy A.
PY - 2017
DA - 2017/04/03
PB - American Chemical Society (ACS)
SP - 4056-4071
IS - 8
VL - 82
PMID - 28328204
SN - 0022-3263
SN - 1520-6904
ER -
BibTex |
Cite this
BibTex (up to 50 authors) Copy
@article{2017_Filimonov,
author = {Valeriy O Filimonov and Lidia N Dianova and Kristina A Galata and Tetyana V Beryozkina and Mikhail S. Novikov and Vera S Berseneva and Oleg S Eltsov and Albert T. Lebedev and Pavel A. Slepukhin and Vasiliy A. Bakulev},
title = {Switchable Synthesis of 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles from 2-Cyanothioacetamides under Diazo Group Transfer Conditions},
journal = {Journal of Organic Chemistry},
year = {2017},
volume = {82},
publisher = {American Chemical Society (ACS)},
month = {apr},
url = {https://pubs.acs.org/doi/10.1021/acs.joc.6b02736},
number = {8},
pages = {4056--4071},
doi = {10.1021/acs.joc.6b02736}
}
MLA
Cite this
MLA Copy
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.” Journal of Organic Chemistry, vol. 82, no. 8, Apr. 2017, pp. 4056-4071. https://pubs.acs.org/doi/10.1021/acs.joc.6b02736.