Copper(I)-photocatalyzed addition of trichloromethanesulfenyl chloride to olefinic compounds

Petek, Nejc (author), Zorko, Tilen (author), Škrinjar, Martin (author), Grošelj, Uroš (author), Svete, Jurij (author), Kočar, Drago (author), Štefane, Bogdan (author)

Atom transfer radical addition (ATRA) reactions are essential transformations in organic synthetic chemistry that enable the atom-economic difunctionalization of abundant olefin feedstocks. In this way, a rich chemical space can be opened up by well-planned combinations of simple starting materials. To build an efficient photocatalytic transformation, the reactivity of trichloromethanesulfenyl chloride toward alkenes and alkynes was investigated under photocatalytic Cu(I) reaction conditions. In this study, we found that trichloromethanesulfenyl chloride can be added to a series of olefins (such as styrenes and electron-rich and -poor olefins) in the presence of 1 mol% [Cu(dmp)$_2$]BF$_4$ photocatalyst and blue LED irradiation, producing α-chloro trichloromethylthioethers in good yields. Experimental and theoretical (DFT) mechanistic studies are consistent with the proposed radical chain mechanism of transformation. This study may serve as a valuable reference for the development of new coupling reactions that are economical and highly efficient processes.

• Language: English
• Keywords: copper photocatalysis, alkenes, sulfenylation, radical chain reaction
• 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: 2025
• Number of pages: 8 str.
• Numbering: Vol. 30, iss. 3, art. 661
• PID: 20.500.12556/RUL-167038
• UDC: 547.1:544.526.5:546.56
• ISSN on article: 1420-3049
• DOI: 10.3390/molecules30030661
• COBISS.SI-ID: 225061891
• Publication date in RUL: 05.02.2025

Record is a part of a journal

• Title: Molecules
• Shortened title: Molecules
• Publisher: MDPI
• ISSN: 1420-3049
• COBISS.SI-ID: 18462981

Licences

• License: CC BY 4.0, Creative Commons Attribution 4.0 International
• Link: http://creativecommons.org/licenses/by/4.0/
• Description: This is the standard Creative Commons license that gives others maximum freedom to do what they want with the work as long as they credit the author.

Secondary language

• Language: Slovenian
• Keywords: fotokataliza, alkeni, sulfenil kloridi, radikalske verižne reakcije

Projects

• Funder: ARIS - Slovenian Research and Innovation Agency
• Project number: P1-0179
• Name: Napredna organska sinteza in kataliza