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

Marharyta V. Laktsevich-Iskryk; Anastasiya V. Krech; Vladimir N. Zhabinskii; Vladimir A. Khripach; Alaksiej L. Hurski

doi:10.1055/s-0040-1706088

Synthesis, Table of Contents

Synthesis 2021; 53(06): 1077-1086
DOI: 10.1055/s-0040-1706088

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

Marharyta V. Laktsevich-Iskryk

,

Anastasiya V. Krech

,

Vladimir N. Zhabinskii

,

Vladimir A. Khripach

,

Alaksiej L. Hurski∗

Abstract

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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 - cyclopropanols - photochemistry - enones - cobaloxime - ring opening

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