Publication:
Activation of DMSO(-d6) via heterogeneous photo-Fenton-like process with in situ production of Hydroxyl radicals for the C-H (trideutero)methylation of (iso)quinoliniums

dc.contributor.departmentKUYTAM (Koç University Surface Science and Technology Center)
dc.contributor.departmentDepartment of Chemistry
dc.contributor.departmentGraduate School of Sciences and Engineering
dc.contributor.kuauthorPalani, Natarajan
dc.contributor.kuauthorMetin, Önder
dc.contributor.kuauthorBaşak, Aleyna
dc.contributor.schoolcollegeinstituteCollege of Sciences
dc.contributor.schoolcollegeinstituteGRADUATE SCHOOL OF SCIENCES AND ENGINEERING
dc.contributor.schoolcollegeinstituteResearch Center
dc.date.accessioned2025-01-19T10:33:09Z
dc.date.issued2023
dc.description.abstractTo activate dimethyl sulfoxide (DMSO, CH3SOCH3) as a methylation agent in the C-H functionalization of (iso)quinoliniums (1), a heterogeneous photo-Fenton-like method involving the in situ generation of hydroxyl radicals by a gCN/MnO/MnO(OH) photocatalyst under visible light irradiation was realized for the first time. In the developed methodology, only a small amount of gCN/MnO/MnO(OH) photocatalysts (15 mg) was needed for the methylation of (iso)quinoliniums (1.0 mmol-scale of 1) to achieve moderate to good yields of the expected methylated-products (2) under ambient conditions. Mechanistically, hydroxyl radicals (OH) are produced when the gCN/MnO/MnO(OH) photocatalyst reacts with H2O and O-2 under visible light illumination, and then they are added to DMSO, where they subsequently fragment into CH3 radicals. The product is generated via the nucleophilic attack of the CH3 radical at the most electron-deficient position of 1, followed by deprotonation reaction. The same procedure could also be used to create trideuteromethylated (iso)quinolines (3) when DMSO-d(6) (CD3SOCD3) was used in place of DMSO. The presented novel strategy for DMSO or DMSO-d(6) activation herein is more practical, cost-effective, and risk-free compared to the conventional Fenton reagent (H2O2 and Fe2+/Fe3+) systems available in the literature. Additionally, the gCN/MnO/MnO(OH) photocatalyst is easy to prepare, practical and economical together with being easy recoverable and reusable for several runs without considerable loss in its initial activity.
dc.description.indexedbyWOS
dc.description.indexedbyScopus
dc.description.issue8
dc.description.publisherscopeInternational
dc.description.sponsoredbyTubitakEuN/A
dc.description.sponsorshipThis research work was financially supported by the Scientific and Technological Research Council of Turkey (TUEBITAK) under the BIDEB Co-Funded Brain Circulation program with a grant no:~121C351. We thank Dr Orhan Altan (Mersin University) for his initial assistance and guidance for the catalyst preparation.
dc.description.volume25
dc.identifier.doi10.1039/d3gc00187c
dc.identifier.eissn1463-9270
dc.identifier.issn1463-9262
dc.identifier.quartileQ1
dc.identifier.scopus2-s2.0-85152101038
dc.identifier.urihttps://doi.org/10.1039/d3gc00187c
dc.identifier.urihttps://hdl.handle.net/20.500.14288/26554
dc.identifier.wos960962000001
dc.keywordsCatalyzed
dc.keywordsMethylation
dc.keywordsDimethyl-sulfoxıde
dc.keywordsAlkylation
dc.keywordsCarbon
dc.keywordsBond
dc.keywordsOxidation
dc.language.isoeng
dc.publisherRoyal Soc Chemistry
dc.relation.grantnoScientific and Technological Research Council of Turkey (TUEBITAK) under the BIDEB Co-Funded Brain Circulation program [~121C351]
dc.relation.ispartofGreen Chemistry
dc.subjectChemistry
dc.titleActivation of DMSO(-d6) via heterogeneous photo-Fenton-like process with in situ production of Hydroxyl radicals for the C-H (trideutero)methylation of (iso)quinoliniums
dc.typeJournal Article
dspace.entity.typePublication
local.contributor.kuauthorMetin, Önder
local.contributor.kuauthorPalani, Natarajan
local.contributor.kuauthorBaşak, Aleyna
local.publication.orgunit1College of Sciences
local.publication.orgunit1GRADUATE SCHOOL OF SCIENCES AND ENGINEERING
local.publication.orgunit1Research Center
local.publication.orgunit2Department of Chemistry
local.publication.orgunit2KUYTAM (Koç University Surface Science and Technology Center)
local.publication.orgunit2Graduate School of Sciences and Engineering
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