An Unusual Rearrangement of Pyrazole Nitrene and Coarctate Ring-Opening/Recyclization Cascade: Formal CH–Acetoxylation and Azide/Amine Conversion without External Oxidants and Reductants-Reference-Cited by-同舟云学术

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

Published:2023-10-30 Issue:21 Volume:28 Page:7335
ISSN:1420-3049
Container-title:Molecules
language:en
Short-container-title:Molecules

Author:

Chugunova Elena¹^ORCID,Gazizov Almir S.¹^ORCID,Islamov Daut¹,Matveeva Victoria¹,Burilov Alexander¹,Akylbekov Nurgali²^ORCID,Dobrynin Alexey¹,Zhapparbergenov Rakhmetulla²,Appazov Nurbol²³^ORCID,Chabuka Beauty K.⁴^ORCID,Christopher Kimberley⁴,Tonkoglazova Daria I.⁴,Alabugin Igor V.¹⁴^ORCID

Affiliation:

1. Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Akad. Arbuzov St. 8, Kazan 420088, Russia

2. Laboratory of Engineering Profile “Physical and Chemical Methods of Analysis”, Korkyt Ata Kyzylorda University, Aitekebie Str. 29A, Kyzylorda 120014, Kazakhstan

3. Zhakhaev Kazakh Scientific Research Institute of Rice Growing, Abay Av. 25B, Kyzylorda 120008, Kazakhstan

4. Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, Tallahassee, FL 32306-3290, USA

Abstract

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–CH3 to R–CH2OC(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.

Funder

the Science Committee of the Ministry of Science and Higher Education of the Republic of Kazakhstan

the Ministry of Science and Higher Education of the Russian Federation at FRC Kazan Scientific Center

government assignment for the FRC Kazan Scientific Center of RAS

Publisher

MDPI AG

Subject

Chemistry (miscellaneous),Analytical Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Molecular Medicine,Drug Discovery,Pharmaceutical Science

Link

https://www.mdpi.com/1420-3049/28/21/7335/pdf

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