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

被引：36

作者：

Mikhailov, Kirill I. ^{[1
]}

Galenko, Ekaterina E. ^{[1
]}

Galenko, Alexey V. ^{[1
]}

Novikov, Mikhail S. ^{[1
]}

Ivanov, Alexander Yu. ^{[1
]}

Starova, Galina L. ^{[1
]}

Khlebnikov, Alexander F. ^{[1
]}

机构：

[1] St Petersburg State Univ, Inst Chem, 7-9 Univ Skaya Nab, St Petersburg 199034, Russia

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2018年 / 83卷 / 06期

基金：

俄罗斯科学基金会;

关键词：

ISOXAZOLES; COMPLEXES; CHEMISTRY; REACTIVITY; OXIDATION; CATALYSTS; AZIRINES; ROUTES; AGENTS;

D O I：

10.1021/acs.joc.8b00069

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

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.

引用

页码：3177 / 3187

页数：11

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