Mild and Regioselective Synthesis of 3-CF3-Pyrazoles by the AgOTf-Catalysed Reaction of CF3-Ynones with Hydrazines

被引：40

作者：

Topchiy, Maxim A. ^{[1
]}

Zharkova, Daria A. ^{[1
,2
]}

Asachenko, Andrey F. ^{[1
]}

Muzalevskiy, Vasiliy M. ^{[2
]}

Chertkov, Vyacheslav A. ^{[2
]}

Nenajdenko, Valentine G. ^{[2
]}

Nechaev, Mikhail S. ^{[1
,2
]}

机构：

[1] Russian Acad Sci, AV Topchiev Inst Petrochem Synth, Leninsky Prospect 29, Moscow, Russia

[2] Moscow MV Lomonosov State Univ, Dept Chem, Moscow 119992, Russia

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2018年 / 2018卷 / 27-28期

基金：

俄罗斯科学基金会;

关键词：

Fluorinated compounds; Nitrogen heterocycles; Fluorine; Regioselectivity; Silver; Pyrazoles; TRIFLUOROMETHYL-BETA-DIKETONES; INTERMOLECULAR HYDROAMINATION; 3+2 CYCLOCONDENSATION; PYRAZOLE; ALKYNES; HYDRAZONES; SOLVENT;

D O I：

10.1002/ejoc.201800208

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Gold- and silver-catalysed reactions of trifluoromethylated ynones with aryl (alkyl) hydrazines were investigated. The use of (THD-Dipp)AuOTf and AgOTf resulted in quick heterocyclization reactions to selectively give 3-CF3-pyrazoles. AgOTf was found to be the catalyst of choice, and various 3-CF3-pyrazoles were formed in up to 99% isolated yield with high regioselectivity. The reaction has a broad scope: 3-CF3-pyrazoles with alkyl and aryl substituents as well as different functional groups can be prepared by this approach. The known pyrazole drugs Celebrex (R) and SC-560 were efficiently prepared to demonstrate the utility of the method. Mechanistic investigations revealed that the reaction involves the formation of a hemiaminal as a key intermediate.

引用

页码：3750 / 3755

页数：6

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