Oxidation of N-trifluoromethylthio sulfoximines using NaOCl [times] 5H [sub] 2O

Žan Testen (Author), Marjan Jereb (Author)

Abstract

N-Trifluoromethylthio sulfoximines are biologically interesting compounds, but their potential is still poorly understood. The oxidation of N-trifluoromethylthio sulfoximines led to their corresponding sulfoxide derivatives as a new class of compounds, when using sodium hypochlorite pentahydrate (NaOCl·5H$_2$O) as a green and relatively unexplored reagent. The reactions took place with a small excess of oxidant under environmentally friendly conditions in EtOAc for 16 h at room temperature. Noteworthy distinctions of this transformation are the simplicity, high selectivity, energy and cost efficiency, minimal amounts of non-hazardous waste, isolation of most of the products without the additional need for chromatographic purification, and simple scalability to gram reactions without deterioration of the yield. The reaction exhibited excellent green chemistry metrics with high atom economy (82.0%), actual atom economy (79.5%), reaction mass efficiency (79.7%), E-factor (16.48) and a very high EcoScale score (84.5). Competitive experiments demonstrated that electron-rich substrates are more reactive than their electron-poor counterparts. Furthermore, the Suzuki–Miyaura functionalization of N-trifluoromethylsulfaneylidene sulfoximine could be achieved depending on the conditions, resulting in coupling products with or without an introduced sulfoxide moiety. Sonogashira coupling of N-trifluoromethylsulfaneylidene sulfoximine furnished the expected acetylene derivative in high yield, and the reaction conditions are compatible with the newly introduced sulfaneylidene functionality. Bromine and nickel catalysts were also shown to be deprotecting agents of the sulfoxide group. A selected N-trifluoromethylsulfaneylidene sulfoximine demonstrated its stability in water in the presence of air and in dilute hydrochloric acid, while it converted back to the parent sulfoximine under basic conditions.

Keywords

trifluorometiltio sulfoksimini;oksidacija;zelena kemija;natrijev hipoklorit pentahidrat;trifluoromethylthio sulfoximines;oxidation;green chemistry;sodium hypochlorite pentahydrate;

Data

Language:	English
Year of publishing:	2024
Typology:	1.01 - Original Scientific Article
Organization:	UL FKKT - Faculty of Chemistry and Chemical Technology
UDC:	547.415.3:542.943
COBISS:	188149507
ISSN:	1477-0539
Views:	46
Downloads:	0
Average score:	0 (0 votes)
Metadata:

Other data

Secondary language:	Slovenian
Secondary keywords:	trifluorometiltio sulfoksimini;oksidacija;zelena kemija;natrijev hipoklorit pentahidrat;
Type (COBISS):	Article
Pages:	str. 2012-2020
Volume:	ǂVol. ǂ22
Issue:	ǂiss. ǂ10
Chronology:	14 Mar. 2024
DOI:	10.1039/d3ob02033a
ID:	24731536