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Blue Light-Promoted Cross-Coupling of α-Diazo Esters with Isocyanides: Synthesis of Ester-Functionalized Ketenimines

[Image: see text] A metal-free scalable synthesis of functionalized ketenimines from alkyl α-(aryl/heteroaryl)-α-diazoacetates and alkyl isocyanides induced by blue light irradiation has been developed. The reaction proceeds at room temperature without any photocatalyst and provides ketenimines in m...

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Detalles Bibliográficos
Autores principales: Sakharov, Pavel A., Novikov, Mikhail S., Nguyen, Tuan K., Kinzhalov, Mikhail A., Khlebnikov, Alexander F., Rostovskii, Nikolai V.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8928522/
https://www.ncbi.nlm.nih.gov/pubmed/35309460
http://dx.doi.org/10.1021/acsomega.2c00367
Descripción
Sumario:[Image: see text] A metal-free scalable synthesis of functionalized ketenimines from alkyl α-(aryl/heteroaryl)-α-diazoacetates and alkyl isocyanides induced by blue light irradiation has been developed. The reaction proceeds at room temperature without any photocatalyst and provides ketenimines in moderate to good yields. Density functional theory (DFT) calculations and the experimental study showed that aryl(alkoxycarbonyl)carbenes in both singlet and triplet states can react with isocyanides but only the reaction of the former leads to the smooth formation of ketenimines. The obtained ketenimines were used for the synthesis of functionalized amidines under mild metal-free conditions.