Theoretical study on the photooxygenation and photorearrangement reactions of 3-hydroxyflavone

Szakács, Zoltán; Kállay, Mihály; Kubinyi, Miklós

doi:10.1039/c7ra04590e

Cited by 12 publications

(10 citation statements)

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“…The only detected photoproducts, 5 and CO, are formed in very high chemical yields; no detectable amounts of photoproduct 6 were found in aerated solutions. The mechanism of the final photooxygenation step has been a subject of investigations with parent flavonol 2 . − ,,− Chou and co-workers proposed that the reaction of triplet phototautomer 3 2Z * with ground-state oxygen takes place via the formation of an endoperoxide intermediate. ,− Recent DFT calculations by Kubinyi and co-workers gave evidence that the addition of 3 O 2 on 3 2Z * gives an endoperoxide and not a hydroperoxide as an intermediate . Inspired by these studies, we show an analogous endoperoxide intermediate 7 , formed upon the reaction of 3 1Z * with ground-state oxygen, in Scheme a; the previously studied mechanism of 2Z photooxygenation is provided in Scheme S1.…”

Section: Resultsmentioning

confidence: 99%

Mechanisms of Orthogonal Photodecarbonylation Reactions of 3-Hydroxyflavone-Based Acid–Base Forms

et al. 2020

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Carbon monoxide is a naturally occurring gasotransmitter combining inherent toxicity with a remarkable therapeutic potential and arduous administration. Photoactivatable carbon monoxide-releasing molecules (photoCORMs) are chemical agents that allow for precise spatial and temporal control over the CO release. In this work, we present a comprehensive mechanistic study of the photochemical CO release from 3-hydroxy-2-phenyl-4H-chromen-4-one, a π-extended 3-hydroxyflavone photoCORM, in methanol using steady-state and transient absorption spectroscopies and quantum chemical calculations. The multiplicity of the productive excited states and the role of oxygen (O2) in the CO production are emphasized, revealing a photoreaction dichotomy of the 3-hydroxyflavone acid and base forms. The utilization of three major orthogonal mechanistic pathways, all of which lead to the CO release, can fuel future endeavors to improve the CO release efficacy of 3-hydroxyflavone-based derivatives and refine their potential medical applications as photoCORMs.

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Section: Resultsmentioning

confidence: 99%

Mechanisms of Orthogonal Photodecarbonylation Reactions of 3-Hydroxyflavone-Based Acid–Base Forms

et al. 2020

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“…A similar reaction pathway has been recently proposed for the photooxygenation of 4′-diethylamino-3-hydroxyflavone [90]. Notably, 3-hydroxyflavone is also known to undergo photoinduced rearrangement in the absence of O 2 (Scheme 15 (bottom)) in apolar, polar aprotic and polar protic solvents, to give a 3-hydroxy-3-aryl-indane-1,2-dione product [91,92,93,94]. In some cases, the indane-1,2-diones releases CO to form a 3-arylphthalide (Scheme 15).…”

Section: Co Production From 3-hydroxyflavones Via Photochemical Rementioning

confidence: 59%

3-Hydroxyflavones and 3-Hydroxy-4-oxoquinolines as Carbon Monoxide-Releasing Molecules

Soboleva

Berreau

2019

Molecules

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Carbon monoxide-releasing molecules (CORMs) that enable the delivery of controlled amounts of CO are of strong current interest for applications in biological systems. In this review, we examine the various conditions under which CO is released from 3-hydroxyflavones and 3-hydroxy-4-oxoquinolines to advance the understanding of how these molecules, or derivatives thereof, may be developed as CORMs. Enzymatic pathways from quercetin dioxygenases and 3-hydroxy-4-oxoquinoline dioxygenases leading to CO release are examined, along with model systems for these enzymes. Base-catalyzed and non-redox-metal promoted CO release, as well as UV and visible light-driven CO release from 3-hydroxyflavones and 3-hydroxy-4-oxoquinolines, are summarized. The visible light-induced CO release reactivity of recently developed extended 3-hydroxyflavones and a 3-hydroxybenzo[g]quinolone, and their uses as intracellular CORMs, are discussed. Overall, this review provides insight into the chemical factors that affect the thermal and photochemical dioxygenase-type CO release reactions of these heterocyclic compounds.

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“…FTIR spectra demonstrate that the C = C stretching band in the keto-enamine linkage of PCOMs was more intense than that of DCOM (Supplementary Fig. 4 ), ascribing to the small energy barriers of enol-keto phototautomerization 33 , 34 . These findings demonstrate a simple and effective strategy for tailoring the crystalline structure of Tp-Byp COM.…”

Section: Resultsmentioning

confidence: 99%

Photo-tailored heterocrystalline covalent organic framework membranes for organics separation

et al. 2022

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Organics separation for purifying and recycling environment-detrimental solvents is essential to sustainable chemical industries. Covalent organic framework (COF) membranes hold great promise in affording precise and fast organics separation. Nonetheless, how to well coordinate facile processing—high crystalline structure—high separation performance remains a critical issue and a grand challenge. Herein, we propose a concept of heterocrystalline membrane which comprises high-crystalline regions and low-crystalline regions. The heterocrystalline COF membranes are fabricated by a two-step procedure, i.e., dark reaction for the construction of high-crystalline regions followed by photo reaction for the construction of low-crystalline regions, thus linking the high-crystalline regions tightly and flexibly, blocking the defect in high-crystalline regions. Accordingly, the COF membrane exhibits sharp molecular sieving properties with high organic solvent permeance up to 44-times higher than the state-of-the-art membranes.

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Theoretical study on the photooxygenation and photorearrangement reactions of 3-hydroxyflavone

Cited by 12 publications

References 50 publications

Mechanisms of Orthogonal Photodecarbonylation Reactions of 3-Hydroxyflavone-Based Acid–Base Forms

Mechanisms of Orthogonal Photodecarbonylation Reactions of 3-Hydroxyflavone-Based Acid–Base Forms

3-Hydroxyflavones and 3-Hydroxy-4-oxoquinolines as Carbon Monoxide-Releasing Molecules

Photo-tailored heterocrystalline covalent organic framework membranes for organics separation

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