Abstract: The introduction of thiocyano groups into organic molecules is important for the preparation of many active ingredients and synthetic intermediates. A commonly used and attractive strategy is the nucleophilic substitution of halogens with the SCN anion or oxidative thiocyanation using an excess amount of external oxidants. A sustainable alternative to stoichiometric reagents is electrochemistry based on anodic oxidation of the SCN anion and other intermediates. Electrochemical thiocyanation of various organic compounds, carried out in the usual non-acidic organic solvents, is well known. Here, we present an electrochemical thiocyanation of 1,3-dicarbonyl compounds in which high efficiency was only achieved using AcOH as the solvent. Electrolysis proceeds in an undivided cell under constant current conditions without any additional halogen-containing electrolytes. Ammonium thiocyanate was used as the source of the SCN group and the electrolyte. Electrochemical thiocyanation of 1,3-dicarbonyl compounds begins with the generation of (SCN)2 from the thiocyanate anion, followed by the addition of thiocyanogen to the double bond of the enol tautomer of 1,3-dicarbonyl compounds, which finally gives the products. A variety of thiocyanated 1,3-dicarbonyl compounds bearing different functional groups were obtained in 37–82% yields and were shown to exhibit high antifungal activity.

Cite: Kirillov A.S. , Semenov E.A. , Bityukov O.V. , Kuznetsova M.A. , Demidova V.N. , Rogozhin A.N. , Glinushkin A.P. , Vil' V.A. , Terent'ev A.O.
An environmentally benign way to synthesize 2-thiocyano-1,3-dicarbonyl compounds with high antifungal activity: a key role of solvent
Organic and Biomolecular Chemistry. 2023. V.21. N17. P.3615-3622. DOI: 10.1039/d3ob00474k WOS Scopus OpenAlex

Identifiers:

Web of science:	WOS:000972179300001
Scopus:	2-s2.0-85153498722
OpenAlex:	W4362683799

Citing:

DB	Citing
OpenAlex	7
Scopus	7
Web of science	6

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