Synthesis of 1,1,3‐Trisubstituted Naphtho[2,3‐<i>c</i>]pyran‐5,10‐dione Derivatives as Potential Redox Switches

Shie, Tien-Lan; Lin, Chi‐Hui; Lin, Shih-Lun; Yang, Ding‐Yah

doi:10.1002/ejoc.200700426

Cited by 12 publications

(2 citation statements)

References 20 publications

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“…To the best of our knowledge, there are no reports on 1,4-naphtho(hydro)quinone compounds containing both an acetylated unit and a thioether unit at the 2,3-positions . Whatever the conditions (electrochemical, chemical, or photochemical conditions) described in the literature or in this study, the reduced naphthoquinone derivatives thus unambiguously correspond to the emitting species. ,, The peculiar emission properties of F-PDO with or without thiols could be thus attributed to an excited-state intramolecular photoinduced transfer (ESIPT) mechanism (keto–enol tautomerization, Figure ) induced by the presence of the benzoyl moiety and the formation of strong hydrogen bonding between the dihydronaphthoquinone core and the acyl residue (Figure ). This ESIPT process can be influenced by the nature of the solvent and has been described for closely related chemical structures such as ortho -hydroxy-acetophenone and derivatives, , 2,5-dihydroxyacetophenone, or 1-hydroxy-2-acetonaphthone, − to cite a few (Figure ).…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Photochemical Properties of Fluorescent Metabolites Generated from Fluorinated Benzoylmenadiones in Living Cells

et al. 2023

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This work describes the reactivity and properties of fluorinated derivatives (F-PD and F-PDO) of plasmodione (PD) and its metabolite, the plasmodione oxide (PDO). Introduction of a fluorine atom on the 2-methyl group markedly alters the redox properties of the 1,4-naphthoquinone electrophore, making the compound highly oxidizing and particularly photoreactive. A fruitful set of analytical methods (electrochemistry, absorption and emission spectrophotometry, and HRMS-ESI) have been used to highlight the products resulting from UV photoirradiation in the absence or presence of selected nucleophiles. With F-PDO and in the absence of nucleophile, photoreduction generates a highly reactive ortho-quinone methide (o-QM) capable of leading to the formation of a homodimer. In the presence of thiol nucleophiles such as β-mercaptoethanol, which was used as a model, o-QMs are continuously regenerated in sequential photoredox reactions generating mono- or disulfanylation products as well as various unreported sulfanyl products. Besides, these photoreduced adducts derived from F-PDO are characterized by a bright yellowish emission due to an excited-state intramolecular proton transfer (ESIPT) process between the dihydronapthoquinone and benzoyl units. In order to evidence the possibility of an intramolecular coupling of the o-QM intermediate, a synthetic route to the corresponding anthrones is described. Tautomerization of the targeted anthrones occurs and affords highly fluorescent stable hydroxyl-anthraquinones. Although probable to explain the intense visible fluorescence emission also observed in tobacco BY-2 cells used as a cellular model, these coupling products have never been observed during the photochemical reactions performed in this study. Our data suggest that the observed ESIPT-induced fluorescence most likely corresponds to the generation of alkylated products through reduction species, as demonstrated with the β-mercaptoethanol model. In conclusion, F-PDO thus acts as a novel (pro)-fluorescent probe for monitoring redox processes and protein alkylation in living cells.

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Section: Resultsmentioning

confidence: 99%

Synthesis and Photochemical Properties of Fluorescent Metabolites Generated from Fluorinated Benzoylmenadiones in Living Cells

et al. 2023

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“…Most molecular fluorescent switching systems operating via a redox couple, consist of a metal-centered redox couple or a luminescent ion core encircled by a macrocyclic receptor . Recently, an “all-organic” donor−acceptor system and chemical and electrochemical fluorescent switches were developed by covalently connecting a fluorophore (the donor, i.e., aminonaphthalene) and an active redox switch (the acceptor, i.e., quinone/hydroquinone) with a conjugated or unconjugated spacer . The fluorescence emission of the donors can be reversibly quenched depending upon the oxidation state of the acceptors.…”

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One-Pot Synthesis of Coumarin-Based Oxazabicyclic and Oxazatricyclic Compounds and Their Fluorescence Redox Switching Properties

2009

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An oxazabicycle and an oxazatricycle were efficiently synthesized by coupling of coumarins and N-alkylquinolium or isoquinolium salt to investigate their fluorescence redox-switching properties. Chemical reduction of the strongly fluorescent oxazabicycle and oxazatricycle results in the ring-opened products with a distinct decrease in emission intensity. Both resulting ring-opened species can be swiftly reverted to the original ring-closed forms by oxidation.

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Click Coupling of Flavylium Dyes with Plasmodione Analogues: Towards New Redox‐Sensitive Pro‐Fluorophores

Dupouy,

Cotos,

Binder

et al. 2024

Chemistry A European J

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The development of redox‐sensitive molecular fluorescent probes for the detection of redox changes in Plasmodium falciparum‐parasitized red blood cells remains of interest due to the limitations of current genetically encoded biosensors. This study describes the design, screening and synthesis of new pro‐fluorophores based on flavylium azido dyes coupled by click chemistry to alkynyl analogues of plasmodione oxide, the key metabolite of the potent redox‐active antimalarial plasmodione. The photophysical and electrochemical properties of these probes were evaluated, focusing on their fluorogenic responses. The influence of the redox status of the quinone and the length of the PEG chain separating the fluorophore from the electrophore on the photophysical properties was investigated. The fluorescence quenching by photoinduced electron transfer is reversible and of high amplitude for probes in oxidized quinone forms and fluorescence is reinstated for reduced hydroquinone forms. Our results demonstrate that shortening the PEG chain has the effect of enhancing the fluorogenic response, likely due to non‐covalent interactions between the two chromophores. All these systems were evaluated for their antiparasitic activities and fluorescence imaging suggests the efficacy of the fluorescent flavylium dyes in P. falciparum‐parasitized red blood cells, paving the way for future parasite imaging studies to monitor cellular redox processes.

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Synthesis of 1,1,3‐Trisubstituted Naphtho[2,3‐c]pyran‐5,10‐dione Derivatives as Potential Redox Switches

Cited by 12 publications

References 20 publications

Synthesis and Photochemical Properties of Fluorescent Metabolites Generated from Fluorinated Benzoylmenadiones in Living Cells

Synthesis and Photochemical Properties of Fluorescent Metabolites Generated from Fluorinated Benzoylmenadiones in Living Cells

One-Pot Synthesis of Coumarin-Based Oxazabicyclic and Oxazatricyclic Compounds and Their Fluorescence Redox Switching Properties

Click Coupling of Flavylium Dyes with Plasmodione Analogues: Towards New Redox‐Sensitive Pro‐Fluorophores

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