Fe(II)-Catalyzed Isomerization of 5-Chloroisoxazoles to 2H-Azirine-2-carbonyl Chlorides as a Key Stage in the Synthesis of Pyrazole-Nitrogen Heterocycle Dyads

Kirill I. Mikhailov, Ekaterina E. Galenko, Alexey V. Galenko, Mikhail S. Novikov, Alexander Yu. Ivanov, Galina L. Starova, Alexander F. Khlebnikov

Research output

12 Citations (Scopus)

Abstract

2-(1H-Pyrazol-1-ylcarbony1)-2H-azirines were synthesized by in situ trapping of 2H-azirine-2-carbonyl chlorides, generated by Fe(II)-catalyzed isomerization of 5-chloroisoxazoles, with pyrazoles. According to DFT calculations, the selectivity of nucleophilic substitution at the carbonyl group of 2H-azirine-2-carbonyl chloride by a pyrazole nucleophile, which is a mixture of two tautomers, is controlled by thermodynamic factors. 2-(1H-Pyrazol-1-ylcarbonyl)-2H-azirines are excellent precursors for the preparation of two other pyrazole nitrogen heterocycle dyads: 5-(1H-pyrazol-1-yl)oxazoles by photolysis and 1-(1H-pyrrol-2-ylcarbonyl)-1H-pyrazoles by a Ni(II)-catalyzed reaction with 1,3-dicarbonyl compounds. 5-(1H-Pyrazol-1-yl)oxazoles show strong emission in acetonitrile at 360-410 nm with high quantum yields.

Original languageEnglish
Pages (from-to)3177-3187
Number of pages11
JournalJournal of Organic Chemistry
Volume83
Issue number6
DOIs
Publication statusPublished - 16 Mar 2018

Cite this

@article{e83e65bbf167450191f5c31457d49137,
title = "Fe(II)-Catalyzed Isomerization of 5-Chloroisoxazoles to 2H-Azirine-2-carbonyl Chlorides as a Key Stage in the Synthesis of Pyrazole-Nitrogen Heterocycle Dyads",
abstract = "2-(1H-Pyrazol-1-ylcarbony1)-2H-azirines were synthesized by in situ trapping of 2H-azirine-2-carbonyl chlorides, generated by Fe(II)-catalyzed isomerization of 5-chloroisoxazoles, with pyrazoles. According to DFT calculations, the selectivity of nucleophilic substitution at the carbonyl group of 2H-azirine-2-carbonyl chloride by a pyrazole nucleophile, which is a mixture of two tautomers, is controlled by thermodynamic factors. 2-(1H-Pyrazol-1-ylcarbonyl)-2H-azirines are excellent precursors for the preparation of two other pyrazole nitrogen heterocycle dyads: 5-(1H-pyrazol-1-yl)oxazoles by photolysis and 1-(1H-pyrrol-2-ylcarbonyl)-1H-pyrazoles by a Ni(II)-catalyzed reaction with 1,3-dicarbonyl compounds. 5-(1H-Pyrazol-1-yl)oxazoles show strong emission in acetonitrile at 360-410 nm with high quantum yields.",
keywords = "ISOXAZOLES, COMPLEXES, CHEMISTRY, REACTIVITY, OXIDATION, CATALYSTS, AZIRINES, ROUTES, AGENTS",
author = "Mikhailov, {Kirill I.} and Galenko, {Ekaterina E.} and Galenko, {Alexey V.} and Novikov, {Mikhail S.} and Ivanov, {Alexander Yu.} and Starova, {Galina L.} and Khlebnikov, {Alexander F.}",
year = "2018",
month = "3",
day = "16",
doi = "10.1021/acs.joc.8b00069",
language = "Английский",
volume = "83",
pages = "3177--3187",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "6",

}

TY - JOUR

T1 - Fe(II)-Catalyzed Isomerization of 5-Chloroisoxazoles to 2H-Azirine-2-carbonyl Chlorides as a Key Stage in the Synthesis of Pyrazole-Nitrogen Heterocycle Dyads

AU - Mikhailov, Kirill I.

AU - Galenko, Ekaterina E.

AU - Galenko, Alexey V.

AU - Novikov, Mikhail S.

AU - Ivanov, Alexander Yu.

AU - Starova, Galina L.

AU - Khlebnikov, Alexander F.

PY - 2018/3/16

Y1 - 2018/3/16

N2 - 2-(1H-Pyrazol-1-ylcarbony1)-2H-azirines were synthesized by in situ trapping of 2H-azirine-2-carbonyl chlorides, generated by Fe(II)-catalyzed isomerization of 5-chloroisoxazoles, with pyrazoles. According to DFT calculations, the selectivity of nucleophilic substitution at the carbonyl group of 2H-azirine-2-carbonyl chloride by a pyrazole nucleophile, which is a mixture of two tautomers, is controlled by thermodynamic factors. 2-(1H-Pyrazol-1-ylcarbonyl)-2H-azirines are excellent precursors for the preparation of two other pyrazole nitrogen heterocycle dyads: 5-(1H-pyrazol-1-yl)oxazoles by photolysis and 1-(1H-pyrrol-2-ylcarbonyl)-1H-pyrazoles by a Ni(II)-catalyzed reaction with 1,3-dicarbonyl compounds. 5-(1H-Pyrazol-1-yl)oxazoles show strong emission in acetonitrile at 360-410 nm with high quantum yields.

AB - 2-(1H-Pyrazol-1-ylcarbony1)-2H-azirines were synthesized by in situ trapping of 2H-azirine-2-carbonyl chlorides, generated by Fe(II)-catalyzed isomerization of 5-chloroisoxazoles, with pyrazoles. According to DFT calculations, the selectivity of nucleophilic substitution at the carbonyl group of 2H-azirine-2-carbonyl chloride by a pyrazole nucleophile, which is a mixture of two tautomers, is controlled by thermodynamic factors. 2-(1H-Pyrazol-1-ylcarbonyl)-2H-azirines are excellent precursors for the preparation of two other pyrazole nitrogen heterocycle dyads: 5-(1H-pyrazol-1-yl)oxazoles by photolysis and 1-(1H-pyrrol-2-ylcarbonyl)-1H-pyrazoles by a Ni(II)-catalyzed reaction with 1,3-dicarbonyl compounds. 5-(1H-Pyrazol-1-yl)oxazoles show strong emission in acetonitrile at 360-410 nm with high quantum yields.

KW - ISOXAZOLES

KW - COMPLEXES

KW - CHEMISTRY

KW - REACTIVITY

KW - OXIDATION

KW - CATALYSTS

KW - AZIRINES

KW - ROUTES

KW - AGENTS

U2 - 10.1021/acs.joc.8b00069

DO - 10.1021/acs.joc.8b00069

M3 - статья

VL - 83

SP - 3177

EP - 3187

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 6

ER -