Molecular Editing of Cycloketones via Deoxygenative Coupling Enabled by Dual Photoexcited Palladium and Photoredox Catalysis
Lixu Ren , Wen Yuan , Long Zhang , Daling Li , Siping Wei , Na Hao , Jun Wang , Lin Yang , Dong Yi , Qiang Fu , Jun Wei , Ji Lu
Chinese Journal of Chemistry ›› 2025, Vol. 43 ›› Issue (17) : 2206 -2212.
Molecular Editing of Cycloketones via Deoxygenative Coupling Enabled by Dual Photoexcited Palladium and Photoredox Catalysis
Herein, we report an unprecedented molecular editing strategy for cycloketones that involves the precise translocation and removal of single oxygen atom enabled by dual photoexcited palladium and photoredox catalysis. In contrast to conventional ketone molecular editing strategies, which often rely on the loss of pre-functionalized groups or the addition of additional acylating agents, this approach facilitates the efficient recycling of pre-functionalized moieties. This is accomplished through a photoexcited palladium catalyzed N–O bond cleavage of cycloketone oxime esters, generating cyanoalkyl radicals and a palladium carboxylate complex. The subsequent photoredox-catalyzed deoxygenation, mediated by phosphoranyl radicals, then leads to the coupling of cyanoalkyl radicals, ultimately yielding the desired products. This molecular editing strategy features good atom economy due to precise skeletal modifications, broad compatibility with various functional groups, and significant potential for late-stage functionalization of pharmaceutical derivatives.
Molecular editing / Cycloketones / Dual catalysis / Photoexcited palladium catalysis / Photoredox catalysis / Acylation
2025 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
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