Oxidation of N-trifluoromethylthio sulfoximines using NaOCl$\cdot$5$H_2O$

Testen, Žan (author), Jereb, Marjan (author)

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.

• Language: English
• Keywords: trifluoromethylthio sulfoximines, oxidation, green chemistry, sodium hypochlorite pentahydrate
• Work type: Article
• Typology: 1.01 - Original Scientific Article
• Organization: FKKT - Faculty of Chemistry and Chemical Technology
• Publication status: Published
• Publication version: Version of Record
• Year: 2024
• Number of pages: Str. 2012-2020
• Numbering: Vol. 22, iss. 10
• PID: 20.500.12556/RUL-160078
• UDC: 547.415.3:542.943
• ISSN on article: 1477-0539
• DOI: 10.1039/d3ob02033a
• COBISS.SI-ID: 188149507
• Publication date in RUL: 16.08.2024

TESTEN, Žan and JEREB, Marjan, 2024, Oxidation of N-trifluoromethylthio sulfoximines using NaOCl▫$\cdot$▫5▫$H_2O$▫. Organic & biomolecular chemistry [online]. 2024. Vol. 22, no. 10, p. 2012–2020. [Accessed 7 April 2025]. DOI 10.1039/d3ob02033a. Retrieved from: https://repozitorij.uni-lj.si/IzpisGradiva.php?lang=eng&id=160078

Record is a part of a journal

• Title: Organic & biomolecular chemistry
• Shortened title: Org. biomol. chem.
• Publisher: Royal Society of Chemistry
• ISSN: 1477-0539
• COBISS.SI-ID: 19836967

Licences

• License: CC BY 3.0, Creative Commons Attribution 3.0 Unported
• Link: https://creativecommons.org/licenses/by/3.0/deed.en
• Description: You are free to reproduce and redistribute the material in any medium or format. You are free to remix, transform, and build upon the material for any purpose, even commercially. You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use. You may not apply legal terms or technological measures that legally restrict others from doing anything the license permits.

Secondary language

• Language: Slovenian
• Keywords: trifluorometiltio sulfoksimini, oksidacija, zelena kemija, natrijev hipoklorit pentahidrat

Projects

• Funder: ARRS - Slovenian Research Agency
• Project number: P1-0230
• Name: Organska kemija: sinteza, struktura in aplikacija

• Funder: ARRS - Slovenian Research Agency
• Funding programme: Young Researchers