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

Autor: Chugunova E; Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Akad. Arbuzov St. 8, Kazan 420088, Russia., Gazizov AS; Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Akad. Arbuzov St. 8, Kazan 420088, Russia., Islamov D; Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Akad. Arbuzov St. 8, Kazan 420088, Russia., Matveeva V; Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Akad. Arbuzov St. 8, Kazan 420088, Russia., Burilov A; Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Akad. Arbuzov St. 8, Kazan 420088, Russia., Akylbekov N; Laboratory of Engineering Profile 'Physical and Chemical Methods of Analysis', Korkyt Ata Kyzylorda University, Aitekebie Str. 29A, Kyzylorda 120014, Kazakhstan., Dobrynin A; Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Akad. Arbuzov St. 8, Kazan 420088, Russia., Zhapparbergenov R; Laboratory of Engineering Profile 'Physical and Chemical Methods of Analysis', Korkyt Ata Kyzylorda University, Aitekebie Str. 29A, Kyzylorda 120014, Kazakhstan., Appazov N; Laboratory of Engineering Profile 'Physical and Chemical Methods of Analysis', Korkyt Ata Kyzylorda University, Aitekebie Str. 29A, Kyzylorda 120014, Kazakhstan.; Zhakhaev Kazakh Scientific Research Institute of Rice Growing, Abay Av. 25B, Kyzylorda 120008, Kazakhstan., Chabuka BK; Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, Tallahassee, FL 32306-3290, USA., Christopher K; Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, Tallahassee, FL 32306-3290, USA., Tonkoglazova DI; Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, Tallahassee, FL 32306-3290, USA., Alabugin IV; Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Akad. Arbuzov St. 8, Kazan 420088, Russia.; Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, Tallahassee, FL 32306-3290, USA.
Jazyk: angličtina
Zdroj: Molecules (Basel, Switzerland) [Molecules] 2023 Oct 30; Vol. 28 (21). Date of Electronic Publication: 2023 Oct 30.
DOI: 10.3390/molecules28217335
Abstrakt: 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.
Databáze: MEDLINE
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