Switchable Synthesis of 4,5-Functionalized 1,2,3-Thiadiazoles and 1,2,3-Triazoles from 2-Cyanothioacetamides under Diazo Group Transfer Conditions / Filimonov Valeriy O.,Dianova Lidia N.,Galata Kristina A.,Beryozkina Tetyana V.,Novikov Mikhail S.,Berseneva Vera S.,Eltsov Oleg S.,Lebedev Albert T.,Slepukhin Pavel A.,Bakulev Vasiliy A. // JOURNAL OF ORGANIC CHEMISTRY. - 2017. - V. 82, l. 8. - P. 4056-4071.

ISSN/EISSN:

0022-3263 / нет данных

Type:

Article

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 S-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 S-sulfonamido-1,2,3-triazole-4-carbothioamide sodium salts as the only products. The latter serve as good precursors for.S-amino-1,2,3-thiadiazole-4-carboxirnidamides, 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.

Author keywords:

MOLECULAR-REARRANGEMENTS; TERMINAL ALKYNES; AZIDES; DERIVATIVES; THIOPHENES; AGENTS

DOI:

10.1021/acs.joc.6b02736

Web of Science ID:

ISI:000400124100006

Соавторы в МНС:

Другие поля

Поле	Значение
Month	APR 21
Publisher	AMER CHEMICAL SOC
Address	1155 16TH ST, NW, WASHINGTON, DC 20036 USA
Language	English
Keywords-Plus	MOLECULAR-REARRANGEMENTS; TERMINAL ALKYNES; AZIDES; DERIVATIVES; THIOPHENES; AGENTS
Research-Areas	Chemistry
Web-of-Science-Categories	Chemistry, Organic
Author-Email	v.a.bakulev@urfu.ru
ORCID-Numbers	Filimonov, Valeriy/0000-0001-6067-7150 Novikov, Mikhail/0000-0001-5106-4723
Funding-Acknowledgement	Russian Science Foundation {[}15-13-10031]
Funding-Text	We gratefully acknowledge financial support of this work by the Russian Science Foundation (15-13-10031). This research was carried out using resources of the Computer Centre of St. Petersburg State University.
Number-of-Cited-References	54
Usage-Count-Last-180-days	10
Usage-Count-Since-2013	12
Journal-ISO	J. Org. Chem.
Doc-Delivery-Number	ET2SJ