An Unusual Rearrangement of Pyrazole Nitrene and Coarctate Ring-Opening/Recyclization Cascade: Formal CH–Acetoxylation and Azide/Amine Conversion without External Oxidants and Reductants

We report an unusual transformation where the transient formation of a nitrene moiety initiates a sequence of steps leading to remote oxidative C–H functionalization (R–CH(3) to R–CH(2)OC(O)R’) and the concomitant reduction of the nitrene into an amino group. No external oxidants or reductants are n...

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Detalles Bibliográficos
Autores principales: Chugunova, Elena, Gazizov, Almir S., Islamov, Daut, Matveeva, Victoria, Burilov, Alexander, Akylbekov, Nurgali, Dobrynin, Alexey, Zhapparbergenov, Rakhmetulla, Appazov, Nurbol, Chabuka, Beauty K., Christopher, Kimberley, Tonkoglazova, Daria I., Alabugin, Igor V.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2023
Materias:
Article
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10648078/
https://www.ncbi.nlm.nih.gov/pubmed/37959754
http://dx.doi.org/10.3390/molecules28217335
Descripción
Sumario:We report an unusual transformation where the transient formation of a nitrene moiety initiates a sequence of steps leading to remote oxidative C–H functionalization (R–CH(3) to R–CH(2)OC(O)R’) and the concomitant reduction of the nitrene into an amino group. No external oxidants or reductants are needed for this formal molecular comproportionation. Detected and isolated intermediates and computational analysis suggest that the process occurs with pyrazole ring opening and recyclization.

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