Synthesis of Pyridylanthracenes and Their Reversible Reaction with Singlet Oxygen to Endoperoxides

Fudickar, Werner; Linker, Torsten

doi:10.1021/acs.joc.7b01765

Cited by 56 publications

(67 citation statements)

References 30 publications

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“…Indeed, anthracene 1c was isolated quantitatively after only 90 min at 25°C (Experimental), in contrast to 1b. [15] Because molecular oxygen is formed partly in its singlet state, such EPOs 2c are mild thermal sources of this reactive intermediate. [25] Very recently, we became interested in EPOs with oxygen substituents 2d (R = OMe) and 2e (R = OAc) (Scheme 2), which are available from their corresponding anthracenes 1d and 1e by photooxygenation in 75-98% yield (Experimental).…”

Section: Results and Discussion Thermolysismentioning

confidence: 99%

“…In analogy to literature, [12][13][14][15][16] the anthracene 1 (1 mmol) was dissolved in chloroform (100 mL) and methylene blue (0.003 g, 0.01 mmol) was added. The solution was cooled to À20°C and irradiated with a sodium lamp (400 W) under passing gaseous oxygen through the solution.…”

Section: General Proceduresmentioning

confidence: 99%

“…156°C (decomposition); R f = 0.33 (CHCl 3 /PE 3:1); 1 H NMR (300 MHz, 9,10-Bis(phenylethynyl)-9,10-dihydro-9,10-epidioxidoanthracene (2c). [15] Reaction of 9,10-bis(phenylethynyl)anthracene (1c, 378 mg, 1 mmol) for 18 h afforded the title compound in 366 mg (89%) without further purification. 9,10-Dimethoxy-9,10-dihydro-9,10-epidioxidoanthracene (2d).…”

Section: General Proceduresmentioning

confidence: 99%

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Intermediates in the cleavage of endoperoxides

Bauch

Klaper

Linker

2016

J of Physical Organic Chem

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The decomposition of anthracene endoperoxides has been investigated under various conditions. Thermolyses proceed via radical intermediates and afford anthracenes and rearrangement products, depending on the substitution pattern. Interestingly, not only the O–O but also the C–O bond can be cleaved homolytically. Under basic conditions fragmentations take place, affording anthraquinone, and reactive oxygen species. This mechanism explains the often observed decomposition of endoperoxides during work‐up. Finally, an acid‐catalyzed cleavage has been observed under release of hydrogen peroxide. The results should be interesting for the mechanistic understanding of peroxide decomposition and the endoperoxides might serve as mild sources of reactive oxygen species for future applications. Copyright © 2016 John Wiley & Sons, Ltd.

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Section: Results and Discussion Thermolysismentioning

confidence: 99%

Section: General Proceduresmentioning

confidence: 99%

Section: General Proceduresmentioning

confidence: 99%

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Intermediates in the cleavage of endoperoxides

Bauch

Klaper

Linker

2016

J of Physical Organic Chem

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“…Bei unserer Methode besteht der Vorteil darin, dass sich das EPO 1 pMe-O 2 zunächst in organischen Lçsungsmitteln in guter Ausbeute synthetisieren lässt [15] und erst danach mit Wasser in Berührung kommt (Schema 2). Bei unserer Methode besteht der Vorteil darin, dass sich das EPO 1 pMe-O 2 zunächst in organischen Lçsungsmitteln in guter Ausbeute synthetisieren lässt [15] und erst danach mit Wasser in Berührung kommt (Schema 2).…”

Section: Angewandte Chemieunclassified

“…[15] Interessanterweise sind die Stabilitäten dieser EPOs verschieden. [15] Interessanterweise sind die Stabilitäten dieser EPOs verschieden.…”

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Chemisch induzierte Freisetzung von Singulettsauerstoff aus aromatischen Endoperoxiden

Fudickar

Linker

2018

Angewandte Chemie

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Die Erzeugung von reaktivem Singulettsauerstoff unter milden Bedingungen ist von aktuellem Interesse in der Chemie,B iologie und Medizin. Durche infachec hemische Induktion kçnnen wir Sauerstoff aus Endoperoxiden (EPOs) bei niedriger Temperatur freisetzen. Tatsächlich beschleunigt die Protonierung und Methylierung von Dipyridylanthracenen solcheR eaktionen stark. Zudem sind die Methylpyridin-Derivate wasserlçslichund dienen somit als Sauerstoffüberträger in wässriger Phase.D ie Methylierung des ortho-Isomers der EPOs erzeugt direkt die ursprünglichen Vorläufer,o hne Erhçhung der Temperatur unter sehr milden Bedingungen. Dieser ungewçhnliche Reaktionsverlauf ist auf den geringen Abstand zwischen dem Stickstoffatom und der Peroxidgruppe zurückzuführen. Der freigesetzte Singulettsauerstoff wurde zur Oxygenierung von Akzeptoren wie Tetramethylethen im Dunkeln bei Raumtemperatur genutzt. Somit haben wir durch einfachec hemische Induktion eine neue Quelle fürS ingulettsauerstoff gefunden.

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Anthracene‐Based Endoperoxides as Self‐Sensitized Singlet Oxygen Carriers for Hypoxic‐Tumor Photodynamic Therapy

He,

Tang

2024

Adv Healthcare Materials

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Singlet oxygen is a crucial reactive oxygen species (ROS) in photodynamic therapy (PDT). However, the hypoxic tumor microenvironment limits the production of cytotoxic singlet oxygen through the light irradiation of PDT photosensitizers (PSs). This restriction poses a major challenge in improving the effectiveness of PDT. To overcome this challenge, researchers have explored the development of singlet oxygen carriers that can capture and release singlet oxygen in physiological conditions. Among these developments, anthracene‐based endoperoxides, initially discovered almost 100 years ago, have shown the ability to generate singlet oxygen controllably under thermal or photo stimuli. Recent advancements have led to the development of a new class of self‐sensitized anthracene‐endoperoxides, with potential applications in enhancing PDT effects for hypoxic tumors. This review discusses the current research progress in utilizing self‐sensitized anthracene‐endoperoxides as singlet oxygen carriers for improved PDT. It covers anthracene‐conjugated small organic molecules, metal–organic complexes, polymeric structures, and other self‐sensitized nano‐structures. The molecular structural designs, mechanisms, and characteristics of these systems will be discussed. This review aims to provide valuable insights for developing high‐performance singlet oxygen carriers for hypoxic‐tumor PDT.

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Synthesis of Pyridylanthracenes and Their Reversible Reaction with Singlet Oxygen to Endoperoxides

Cited by 56 publications

References 30 publications

Intermediates in the cleavage of endoperoxides

Intermediates in the cleavage of endoperoxides

Chemisch induzierte Freisetzung von Singulettsauerstoff aus aromatischen Endoperoxiden

Anthracene‐Based Endoperoxides as Self‐Sensitized Singlet Oxygen Carriers for Hypoxic‐Tumor Photodynamic Therapy

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