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

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

Publication History

Received: 30 September 2020

Accepted after revision: 30 October 2020

Article published online:
01 December 2020

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