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Bimal Pudasaini
분자활성 촉매반응 연구단
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Oxidation of Cymantrene-Tagged Tamoxifen Analogues: Effect of Diphenyl Functionalization on the Redox Mechanism

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Title
Oxidation of Cymantrene-Tagged Tamoxifen Analogues: Effect of Diphenyl Functionalization on the Redox Mechanism
Author(s)
Kan Wu; Bimal Pudasaini; Ji Young Park; Siden Top; Gérard Jaouen; Mu-Hyun Baik; William E. Geiger
Publication Date
2020-03
Journal
ORGANOMETALLICS, v.39, no.5, pp.679 - 687
Publisher
AMER CHEMICAL SOC
Abstract
© 2020 American Chemical Society.The oxidations of 1,1′-di-p-anisolyl-2-cymantrenylbutene (3b) and 1,1′-di-p-hydroxyphenyl-2-cymantrenylbutene (3c) were investigated by electrochemical and spectroscopic experiments and by density functional theory (DFT) calculations. Both compounds undergo a reversible one-electron oxidation followed closely by a partially chemically reversible second oxidation (E1/2 values vs ferrocene: 0.60 and 0.74 V for 3b; 0.63 and 0.78 V for 3c). In comparison to the nonphenyl-functionalized parent, 1,1′-diphenyl-2-cymantrenylbutene (3a), 3b,c have lower and more closely spaced oxidation potentials and more rapid follow-up reactions of their dications, 3b2+ and 3c2+. Shifts in the calculated charge distributions of the neutral compounds and their singly and doubly oxidized products corroborated trends in the measured shifts of Mn-CO νCO frequencies in assigning the redox sites primarily to the diarylbutene fragment. Upon removal of electrons, the lost charge density is partially compensated by the polarizable cymantrenyl tag. The half-lives of the dications 3b2+ and 3c2+ are about 10 s at room temperature in dichloromethane/0.05 M [NBu4][B(C6F5)4]. Their follow-up reactions are initiated by loss of a proton either from a hydroxyl group or from the CH2 group of the diarylbutene unit, giving rise to two products having quinone methide structures. Although the initial oxidation sites of cymantrene-tagged diarylbutenes are primarily ligand based and those of ferrocene-tagged diarylbutenes are metal-based, the ultimate oxidation products of their p-OH- or p-OMe-functionalized derivatives are very similar
URI
https://pr.ibs.re.kr/handle/8788114/7138
ISSN
0276-7333
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > Journal Papers (저널논문)
Files in This Item:
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