Self-Sensitized Photooxygenation of 3,4-Dialkoxyfurans to Vitamin C or Its Derivatives

Hakimelahi, G. H.; Jain, M.; Ly, Tai Wei; Chen, I-Chia; Ethiraj, K. S.; Hwu, Jih Ru; Moshfegh, Ali A.

doi:10.1021/jo010531l

Cited by 8 publications

(3 citation statements)

References 17 publications

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“…Thus, the reaction sequence for the formation of 2 involves a one-pot three steps domino process (isomerization, hetero-electrocyclization and [2+4] Diels-Alder type oxygen addition) (36), representing an improved procedure for the preparation of 1,2,4-trioxane-type compounds. The formation in less proportion of the 5,8-endoperoxide 5 by direct reaction of 1 with 1 O 2 was also observed, and the relative distribution of oxygenated products [2] ⁄ [5] is controlled by the ratio k r,3 [3] ⁄ k r,1 [1].…”

Section: Discussionmentioning

confidence: 99%

“…The reaction of 1 O 2 with the singlet ground state of organic molecules is so specialized that examples of spontaneous addition of 3 O 2 are rare. However, certain types of olefinic compounds undergo light‐induced oxidation without dye sensitizer, and in those cases self‐photosensitized oxygenation mechanisms have been proposed to rationalize the formation of the oxygenated products (5,6).…”

Section: Introductionmentioning

confidence: 99%

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UVA Self‐Photosensitized Oxygenation of β‐Ionone

Borsarelli

Mischne

La–Venia

et al. 2007

Photochem & Photobiology

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The steady-state UVA (350 nm) photolysis of (E)-beta-ionone (1) in aerated toluene solutions was studied by (1)H NMR spectroscopy. The formation of the 1,2,4-trioxane (2) and 5,8-endoperoxide (5) derivatives in the ratio of 4:1 was observed. Time-resolved laser induced experiments at 355 nm, such as laser-flash photolysis, photoacoustic and singlet oxygen (1)O(2) phosphorescence detection, confirmed the formation of the excited triplet state of 1 with a quantum yield Phi(T) = 0.50 as the precursor for the generation of singlet oxygen (1)O(2) (Phi(Delta) = 0.16) and the isomeric alpha-pyran derivative (3), which was a reaction intermediate detected by NMR. In turn, the reaction of (1)O(2) with 1 and 3 occurred with rate constants of 1.0 x 10(6) and 2.5 x 10(8) M(-1)s(-1) to yield the oxygenated products 5 and 2, respectively, indicating the relevance of the fixed s-cis configuration in the alpha-pyran ring in the concerted [2+4] cycloaddition of (1)O(2).

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

UVA Self‐Photosensitized Oxygenation of β‐Ionone

Borsarelli

Mischne

La–Venia

et al. 2007

Photochem & Photobiology

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“…Very few and specific examples have been described to generate 1 O 2 via self-sensitization under visible light activation. These are mostly related to large polyaromatic compounds such as bilirubin, fullerenes, − or dimethyldihydropyrene derivatives, , while examples of the self-sensitization of smaller molecules remain very limited. − …”

Section: Introductionmentioning

confidence: 99%

Self-Sensitized Photooxidation of Naphthols to Naphthoquinones and the Use of Naphthoquinones as Visible Light Photocatalysts in Batch and Continuous Flow Reactors

et al. 2023

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Visible light photooxidation of naphthols to produce naphthoquinones, such as the natural product juglone, has been known for decades and has been widely utilized to benchmark the performances of a variety of photocatalytic systems. We discovered that these transformations can occur without the help of a photocatalyst and, even more intriguingly, that the photocatatyst-free process provides higher yields compared to control experiments utilizing state-of-the-art photocatalysts. In addition, we demonstrate that naphthoquinones and their corresponding naphthol precursors can act as alternatives to commonly used organic and organometallic photocatalysts with applications to challenging targets, such as the antimalarial drug artemisinin. This approach was finally transposed in continuous flow reactors where high photocatalyst stability and process efficiency are demonstrated with a 23× improvement in the space-time yield.

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Singlet Oxygen Responsive Molecular Receptor to Modulate Atropisomerism and Cation Binding

Bouteille

Sonet

Hennebelle

et al. 2023

Chemistry A European J

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In switchable molecular recognition, 1O2 stimulus responsive receptors offer a unique structural change that is rarely exploited. The employed [4+2] reaction between 1O2 and anthracene derivatives is quantitative, reversible and easily implemented. To evaluate the full potential of this new stimulus, a non‐macrocyclic anthracene‐based host was designed for the modular binding of cations. The structural investigation showed that 1O2 controlled the atropisomerism in an on/off fashion within the pair of hosts. The binding studies revealed higher association constants for the endoperoxide receptor compared to the parent anthracene, due to a more favoured preorganization of the recognition site. The fatigue of the 1O2 switchable hosts and their complexes was monitored over five cycles of cycloaddition/cycloreversion.

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Self-Sensitized Photooxygenation of 3,4-Dialkoxyfurans to Vitamin C or Its Derivatives

Cited by 8 publications

References 17 publications

UVA Self‐Photosensitized Oxygenation of β‐Ionone

UVA Self‐Photosensitized Oxygenation of β‐Ionone

Self-Sensitized Photooxidation of Naphthols to Naphthoquinones and the Use of Naphthoquinones as Visible Light Photocatalysts in Batch and Continuous Flow Reactors

Singlet Oxygen Responsive Molecular Receptor to Modulate Atropisomerism and Cation Binding

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