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An Unusual Rearrangement of Pyrazole Nitrene and Ring Opening/Recyclization Cascade: Formal CH-Acetoxylation and Azide/Amine Conversion without External Oxidants and Reductants
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. Molecules2023, 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.
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. Molecules2023, 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.
Chemistry and Materials Science, Organic Chemistry
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