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

共 50 条

[31] Controllable Regioselective [3+2] Cyclizations of N-CF3 Imidoyl Chlorides and Ph3PNNC: Divergent Synthesis of N-CF3 Triazoles
Gao, Yan Fang
Zhang, Ru Zhong
Xu, Cong
Wang, Mang
ORGANIC LETTERS, 2024, : 5087 - 5091
[32] Temperature dependent kinetics of the reaction OH+CF3CH2CF3
Garland, NL
Nelson, HH
CHEMICAL PHYSICS LETTERS, 1996, 248 (3-4) : 296 - 300
[33] Regioselective Synthesis of Functionalized 3-or 5-Fluoroalkyl Isoxazoles and Pyrazoles from Fluoroalkyl Ynones and Binucleophiles
Chalyk, Bohdan A.
Khutorianskyi, Andrii
Lysenko, Andrii
Fil, Yulia
Kuchkovska, Yuliya O.
Gavrilenko, Konstantin S.
Bakanovych, Iulia
Moroz, Yurii S.
Gorlova, Alina O.
Grygorenko, Oleksandr O.
JOURNAL OF ORGANIC CHEMISTRY, 2019, 84 (23): : 15212 - 15225
[34] DIRECT SYNTHESIS OF FLUORINATED PEROXIDES .8. SYNTHESIS AND PROPERTIES OF (CF3)3COOF AND EVIDENCE FOR TRIOXIDE (CF3)3COOOC(CF3)3
YU, SL
DESMARTEAU, DD
INORGANIC CHEMISTRY, 1978, 17 (09) : 2484 - 2487
[35] Crystal structure of CF3TeTeCF3. Synthesis, characterization, and properties of CF3TeI
Dukat, W
Gall, F
Meyer, C
Mootz, D
Naumann, D
Nowicki, G
Schultz, K
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 1996, 622 (04): : 617 - 621
[36] SYNTHESIS OF THE UNSYMMETRICAL DISELENANES CF3SESECF2CL AND CF3SESECH3
GOMBLER, W
BOLLMANN, G
JOURNAL OF FLUORINE CHEMISTRY, 1987, 37 (01) : 15 - 20
[37] A convenient nucleophilic method for the synthesis and radiosynthesis of CF3 and [18F]CF3-groups under mild conditions
Riss, Patrick J.
Aigbirhio, Franklin, I
JOURNAL OF LABELLED COMPOUNDS & RADIOPHARMACEUTICALS, 2011, 54 : S516 - S516
[38] Exercise in 1-aryl-3-CF3-1H-pyrazoles: regioselective synthesis of 4-/5-iodides and cross-coupling reactions
Swiatek, Kamil
Utecht-Jarzynska, Greta
Jasinski, Marcin
RSC ADVANCES, 2025, 15 (12) : 9225 - 9229
[39] Theoretical studies on the reaction mechanism of CF3CF=CF2 with OH
Ai, Li-ling
Duan, Xue-mei
Liu, Jing-yao
COMPUTATIONAL AND THEORETICAL CHEMISTRY, 2013, 1013 : 15 - 22
[40] REACTION OF METAL FLUORIDES WITH CF3OOCF2N(H)CF3
SEKIYA, A
DESMARTEAU, DD
INORGANIC CHEMISTRY, 1979, 18 (04) : 919 - 920

← 1 2 3 4 5 →