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
收藏
页码：3750 / 3755
页数：6
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