Regioselectivity Patterns in Radical Cyclization of Diosphenol Derivatives with Different Ring Size: A Combined Experimental and DFT Study

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dc.authoridZaim, Omer/0000-0002-3472-5611
dc.authoridTuzun, Nurcan/0000-0001-5225-3876
dc.authoridOzcan, hafize/0000-0002-8031-6755
dc.authorwosidZaim, Omer/Q-7770-2019
dc.authorwosidTuzun, Nurcan/N-9217-2013
dc.authorwosidOzcan, hafize/KJM-5364-2024
dc.contributor.authorBoz, Esra
dc.contributor.authorozcan, Hafize
dc.contributor.authorZaim, Omer
dc.contributor.authorTuzun, Nurcan S.
dc.date.accessioned2024-06-12T10:59:24Z
dc.date.available2024-06-12T10:59:24Z
dc.date.issued2021
dc.departmentTrakya Üniversitesien_US
dc.description.abstractRadical cyclization reactions are still a challenging field in synthetic organic chemistry. Herein, the radical reactions of 6- and 7-membered diosphenol derivatives (tropolone) with a significant difference in reactivity, ring size, aromaticity and stability were investigated. While the former produces a mixture of products including oxabicycloalkanones, the experimental work performed herein resulted with a single 2-(3-hydroxypropyl)cyclohepta-2,4,6-trienone product, regioselectively. DFT calculations (UM05/6-311++G(d,p)) were performed following the experimental studies in order to describe the outcomes correctly. Therefore, all possible reaction pathways were investigated for both diosphenol and tropolone. The reaction barriers and intrinsic barriers from the Marcus theory were calculated to investigate the thermodynamic and intrinsic electronic effects to the experimental product distribution. Both experiment and theory show that the aforementioned systems have different selectivity routes governed by several factors. As a result of this comparative study, the charge distribution at the reactive atoms, entropy factors for cyclization vs termination and aromatization of the ring effects were found to be the driving factors for the observed regioselectivity.en_US
dc.description.sponsorshipNational High Performance Computing Center at Istanbul Technical University [5004722017]; ITU BAP Project [39944]; project commission of Trakya University [TUBAP 2013/69]en_US
dc.description.sponsorshipWe gratefully acknowledge the computational source provided by the National High Performance Computing Center at Istanbul Technical University (Grant No: 5004722017); ITU BAP Project (Grant No. 39944) and project commission of Trakya University (TUBAP 2013/69) for financial support. The calculations reported in this paper were partially performed at TUBITAK ULAKBIM, High Performance and Grid Computing Center (TRUBA resources).en_US
dc.identifier.doi10.1002/slct.202004601
dc.identifier.endpage1755en_US
dc.identifier.issn2365-6549
dc.identifier.issue8en_US
dc.identifier.scopus2-s2.0-85101505935en_US
dc.identifier.scopusqualityQ2en_US
dc.identifier.startpage1748en_US
dc.identifier.urihttps://doi.org/10.1002/slct.202004601
dc.identifier.urihttps://hdl.handle.net/20.500.14551/20431
dc.identifier.volume6en_US
dc.identifier.wosWOS:000621116700003en_US
dc.identifier.wosqualityQ3en_US
dc.indekslendigikaynakWeb of Scienceen_US
dc.indekslendigikaynakScopusen_US
dc.language.isoenen_US
dc.publisherWiley-V C H Verlag Gmbhen_US
dc.relation.ispartofChemistryselecten_US
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanıen_US
dc.rightsinfo:eu-repo/semantics/closedAccessen_US
dc.subjectDFTen_US
dc.subjectDiosphenolen_US
dc.subjectEndo-Exo Selectivityen_US
dc.subjectRadical Cyclizationen_US
dc.subjectRegioselectivityen_US
dc.subjectTropoloneen_US
dc.subjectMarcus Theoryen_US
dc.subjectMechanismen_US
dc.subjectClosureen_US
dc.subjectCyclopolymerizationen_US
dc.subjectPathen_US
dc.subjectStereoselectivityen_US
dc.subjectFragmentationsen_US
dc.subjectDiallylamineen_US
dc.subjectCompetitionen_US
dc.subjectOxidationen_US
dc.subjectMonomersen_US
dc.titleRegioselectivity Patterns in Radical Cyclization of Diosphenol Derivatives with Different Ring Size: A Combined Experimental and DFT Studyen_US
dc.typeArticleen_US

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