Photocatalytic Stoichiometric Oxidant-Free Synthesis of Linear Unsaturated Ketones from 1,2-Disubstituted Cyclopropanols

Autor:	Vladimir A. Khripach, Anastasiya V. Krech, Marharyta V. Laktsevich-Iskryk, Alaksiej L. Hurski, Vladimir N. Zhabinskii
Rok vydání:	2020
Předmět:	010405 organic chemistry Chemistry Organic Chemistry 010402 general chemistry Ring (chemistry) Photochemistry 01 natural sciences Catalysis 0104 chemical sciences chemistry.chemical_compound Cyclopropanol Air atmosphere Photocatalysis Irradiation Stoichiometry Visible spectrum
Zdroj:	Synthesis. 53:1077-1086
ISSN:	1437-210X 0039-7881
DOI:	10.1055/s-0040-1706088
Popis:	A one-step catalytic oxidant-free synthesis of unsaturated ketones from 1,2-disubstituted cyclopropanols is reported. Previously for this transformation, only two- and three-step protocols have been developed. The reaction proceeds under irradiation with visible light in the presence of catalytic amounts of both an acridinium photocatalyst and a cobaloxime complex. 2-Aryl-substituted cyclopropanols react giving α,β-unsaturated ketones, while dehydrogenative ring opening of 2-alkyl-substituted substrates affords mixtures of α,β- and β,γ-enones. The reaction starts with one-electron oxidation of a cyclopropanol to cyclopropyloxy radical, presumably, by the photoexcited acridinium catalyst. We also found that Co(dmgBF2)2(MeCN)2 complex under an air atmosphere and irradiation with blue LEDs or upon heating can serve as a hydroxycyclopropane oxidant.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::678cc0eb0c6296a09e3a2a3311511a64 https://doi.org/10.1055/s-0040-1706088 Zobrazit plný text záznamu