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Synthesis 2021; 53(06): 1077-1086
DOI: 10.1055/s-0040-1706088
DOI: 10.1055/s-0040-1706088
feature
Photocatalytic Stoichiometric Oxidant-Free Synthesis of Linear Unsaturated Ketones from 1,2-Disubstituted Cyclopropanols
This work was funded by the Belarussian Republican Foundation for Fundamental Research (project Х20М-036).
Abstract
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.
Key words
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cyclopropanols -
photochemistry -
enones -
cobaloxime -
ring opening
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1706088.
- Supporting Information
Publication History
Received: 30 September 2020
Accepted after revision: 30 October 2020
Article published online:
01 December 2020
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