Activation of Anthraquinone's Electrophilicity by Light for a Dynamic C-O Bond.

Autor: Bykov VN; A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Street, Irkutsk, 664033, Russia.; Irkutsk National Research Technical University, 83 Lermontov Street, Irkutsk, 664074, Russia., Ukhanev SA; A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Street, Irkutsk, 664033, Russia., Ushakov IA; A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Street, Irkutsk, 664033, Russia., Vologzhanina AV; A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Science, 28 Vavilova Street, Moscow, 119991, Russia., Antsiferov EA; Irkutsk National Research Technical University, 83 Lermontov Street, Irkutsk, 664074, Russia., Klimenko LS; Yugra State University, 16 Chekhov Street, Khanty-Mansiysk, 628012, Russia., Lvov AG; A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Street, Irkutsk, 664033, Russia.; Irkutsk National Research Technical University, 83 Lermontov Street, Irkutsk, 664074, Russia.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2024 Jan 24; Vol. 146 (3), pp. 1799-1805. Date of Electronic Publication: 2024 Jan 11.
DOI: 10.1021/jacs.3c12461
Abstrakt: Coupling of photoswitching with dynamic covalent chemistry enables control of the formation and cleavage of covalent bonds by light irradiation. peri -Aryloxyanthraquinones feature an exclusive ability to switch electrophilicity by interconversion between para - and ana -quinone isomers, which was used for the first time for the implementation of a dynamic C-O bond. Photogenerated ana -isomers undergo a concerted oxa -Michael addition of phenols to give hitherto unknown 4-hydroxy-10,10-diaryloxyanthracen-9-ones. These species were found to be in equilibrium with the corresponding ana -quinones, thus forming a dynamic covalent system of a new type. Withdrawal of the colored ana -quinones from the equilibria by visible light irradiation resulted in two para -quinones with "locked" aryloxy groups.
Databáze: MEDLINE