Molecular photonics of dienones based on cycloalkanones and their derivatives

Gutrov, V. N.; Захарова, Г. В.; Fomina, M. V.; Nuriev, V. N.; Gromov, S. P.; Чибисов, А. К.

doi:10.1016/j.jphotochem.2021.113678

Cited by 7 publications

(7 citation statements)

References 52 publications

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“…In the unsubstituted dienone 1a, the dark n -π* state lies below the bright π-π* state, which results in the lack of emission. Previously, we observed a similar picture in a cyclohexanone analog of dienone 1a and attributed its lack of fluorescence to the same reason [ 35 , 42 ].…”

Section: Resultssupporting

confidence: 61%

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Synthesis, Structure and Photochemistry of Dibenzylidenecyclobutanones

et al. 2022

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A series of symmetrical dibenzylidene derivatives of cyclobutanone were synthesized with the goal of studying the physicochemical properties of cross-conjugated dienones (ketocyanine dyes). The structures of the products were established and studied by X-ray diffraction and by NMR and electronic spectroscopy. All the products had E,E-geometry. The oxidation and reduction potentials of the dienones were determined by cyclic voltammetry. The potentials were shown to depend on the nature, position, and number of substituents in the benzene rings. A linear correlation was found between the difference of the electrochemical oxidation and reduction potentials and the energy of the long-wavelength absorption maximum. This correlation can be employed to analyze the properties of other compounds of this type. Quantum chemistry was used to explain the observed regularities in the electrochemistry, absorption, and fluorescence of the dyes. The results are in good agreement with the experimental redox potentials and spectroscopy data.

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Section: Resultssupporting

confidence: 61%

“…The absorption and emission of compound 1f and its aza-crown ether analog are described in detail elsewhere [ 42 ].…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Structure and Photochemistry of Dibenzylidenecyclobutanones

et al. 2022

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“…The fluorescence of the dyes deserves a special discussion. Unlike cyclobutanone and cyclopentanone dyes, only 1e and 1f show noticeable fluorescence. Our calculations explain this fact (Table ).…”

Section: Results and Discussionmentioning

confidence: 96%

Structure–Property Relationships of Dibenzylidenecyclohexanones

et al. 2022

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A series of symmetrical dibenzylidene derivatives of cyclohexanone were synthesized with the goal of studying the physicochemical properties of cross-conjugated dienones (ketocyanine dyes). The structures of the products were established and studied by X-ray diffraction, NMR spectroscopy, and electronic spectroscopy. All products had the E , E -geometry. The oxidation and reduction potentials of the dienones were determined by cyclic voltammetry. The potentials were shown to depend on the nature, position, and number of substituents in the benzene rings. A linear correlation was found between the difference of the electrochemical oxidation and reduction potentials and the energy of the long-wavelength absorption maximum. This correlation can be employed to analyze the properties of other compounds of this type. The frontier orbital energies and the vertical absorption and emission transitions were calculated using quantum chemistry. The results are in good agreement with experimental redox potentials and spectroscopic data.

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“…Indeed, we observed a weak absorption band at λ max = 348 nm in the ultravioletvisible (UV/Vis) spectrum of molephantin (1) in CH 2 Cl 2 (0.5 mM), which was characterized as the n-π* transition of the carbonyl group of the dienone moiety (see the Supporting Information). [40] We found that irradiation of a solution of 1 in degassed CH 2 Cl 2 with ultraviolet A light (λ max = 370 nm) could generate multiple alkene isomers within a few minutes, as confirmed by the 1 H NMR analyses, suggesting that the dienone isomers (E,E)-1, (Z,E)-1 and (Z,Z)-1 could be formed under photoequilibrium. We observed that these dienone congeners could eventually converge to 25 in a quantitative yield via hemiketalization of (Z,Z)-1.…”

Section: Methodsmentioning

confidence: 60%

“… [35] Inspired by the previous studies on photochemical isomerization of dienone‐based sesquiterpene natural products such as tagitinin C, [36] asteriscunolide D [37] and zerumbone [38,39] under irradiation with UV light, we investigated the analogous photochemical dienone‐isomerization of molephantin ( 1 ). Indeed, we observed a weak absorption band at λ max =348 nm in the ultraviolet‐visible (UV/Vis) spectrum of molephantin ( 1 ) in CH 2 Cl 2 (0.5 mM), which was characterized as the n‐π* transition of the carbonyl group of the dienone moiety (see the Supporting Information) [40] . We found that irradiation of a solution of 1 in degassed CH 2 Cl 2 with ultraviolet A light (λ max =370 nm) could generate multiple alkene isomers within a few minutes, as confirmed by the 1 H NMR analyses, suggesting that the dienone isomers ( E , E )‐ 1 , ( Z , E )‐ 1 and ( Z , Z )‐ 1 could be formed under photoequilibrium.…”

Section: Figurementioning

confidence: 99%

Collective Synthesis of Highly Oxygenated (Furano)germacranolides Derived from Elephantopus mollis and Elephantopus tomentosus

Patouret,

Cham,

Chiba

2024

Angewandte Chemie

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Germacranolides, secondary metabolites produced by plants, have garnered academic and industrial interest due to their diverse and complex topology as well as a wide array of pharmacological activities. Molephantin, a highly oxygenated germacranolide isolated from medicinal plants, Elephantopus mollis and Elephantopus tomentosus, has exhibited anti‐tumor, inflammatory, and leishmanicidal activities. Its chemical structure is based on a highly strained ten‐membered macrocyclic backbone with an (E,Z)‐dienone moiety, which is fused with an α‐methylene‐γ‐butyrolactone and adorned with four successive stereogenic centers. Herein, we report the first synthesis of molephantin via 12 steps starting from readily available building blocks. The synthesis features the highly diastereoselective intermolecular Barbier allylation of the β,γ‐unsaturated aldehyde with optically active 3‐bromomethyl‐5H‐furan‐2‐one intermediate and ensuing Nozaki‐Hiyama‐Kishi (NHK) macrocyclization for the construction of the highly oxygenated ten‐membered macrocyclic framework. This synthetic route enabled access to another germacranolide congener, tomenphantopin F. Furthermore, cycloisomerization of molephantin into 2‐deethoxy‐2β‐hydroxyphantomolin could be facilitated by irradiation with ultraviolet A light (λmax = 370 nm), which opened a versatile and concise access to the related furanogermacranolides such as EM‐2, phantomolin, 2‐O‐demethyltomephantopin C, and tomenphantopin C.

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Molecular photonics of dienones based on cycloalkanones and their derivatives

Cited by 7 publications

References 52 publications

Synthesis, Structure and Photochemistry of Dibenzylidenecyclobutanones

Synthesis, Structure and Photochemistry of Dibenzylidenecyclobutanones

Structure–Property Relationships of Dibenzylidenecyclohexanones

Collective Synthesis of Highly Oxygenated (Furano)germacranolides Derived from Elephantopus mollis and Elephantopus tomentosus

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