Preprint Article Version 1 Preserved in Portico This version is not peer-reviewed

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

Elena Chugunova
* ORCID logo ,
Almir S Gazizov
ORCID logo ,
Daut Islamov
,
Victoria Matveeva
,
Alexander Burilov
,
Nurgali Akylbekov
ORCID logo ,
Alexey Dobrynin
,
Rakhmetulla Zhapparbergenov
,
Nurbol Appazov
* ORCID logo ,
Beauty K. Chabuka
,
Kimberley Christopher
,
Daria I. Tonkoglazova
,
Igor Alabugin
Version 1 : Received: 9 October 2023 / Approved: 9 October 2023 / Online: 9 October 2023 (10:24:39 CEST)

A peer-reviewed article of this Preprint also exists.

Chugunova, E.; Gazizov, A.S.; Islamov, D.; Matveeva, V.; Burilov, A.; Akylbekov, N.; Dobrynin, A.; Zhapparbergenov, R.; Appazov, N.; Chabuka, B.K.; Christopher, K.; Tonkoglazova, D.I.; Alabugin, I.V. An Unusual Rearrangement of Pyrazole Nitrene and Coarctate Ring-Opening/Recyclization Cascade: Formal CH–Acetoxylation and Azide/Amine Conversion without External Oxidants and Reductants. Molecules 2023, 28, 7335. Chugunova, E.; Gazizov, A.S.; Islamov, D.; Matveeva, V.; Burilov, A.; Akylbekov, N.; Dobrynin, A.; Zhapparbergenov, R.; Appazov, N.; Chabuka, B.K.; Christopher, K.; Tonkoglazova, D.I.; Alabugin, I.V. An Unusual Rearrangement of Pyrazole Nitrene and Coarctate Ring-Opening/Recyclization Cascade: Formal CH–Acetoxylation and Azide/Amine Conversion without External Oxidants and Reductants. Molecules 2023, 28, 7335.

Abstract

We report an unusual transformation where a transient formation of a nitrene moiety initiates a sequence of steps where leading to a remote oxidative C-H functionalization (R-CH3 to R-CH2OC(O)R’) and concomitant reduction of the nitrene into an amino group. No external oxi-dants or reductants are needed for this formal molecular com-proportionation. Detected and iso-lated intermediates and computational analysis suggest that the process occurs with pyrazole ring opening and recyclization.

Keywords

furoxan; 1H-pyrazole; nitrene; fragmentation; cyclization

Subject

Chemistry and Materials Science, Organic Chemistry

Copyright: This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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