- Study on the green click-chemistry synthesis of 4-trifluoroacetyl-1,2,3-triazoles
-
A metal-free and solvent free click-chemistry procedure has been revealed for the synthesis of 4-trifluoroacetyl-1,2,3-triazoles from corresponding azides and alkyne with high yield and selectivity. The pure products could be easily obtained via crystalli
- Han, Jie,Ran, Jian-Xiong,Chen, Xiu-Ping,Wang, Zhong-Hua,Wu, Fan-Hong
-
-
Read Online
- Direct Catalytic Asymmetric Vinylogous Additions of α,β- and β,γ-Butenolides to Polyfluorinated Alkynyl Ketimines
-
We report a Zn-ProPhenol catalyzed asymmetric Mannich reaction between butenolides and polyfluorinated alkynyl ketimines to obtain vinylogous products featuring two contiguous tetrasubstituted stereogenic centers. Notably, this is the first successful use
- Trost, Barry M.,Hung, Chao-I. (Joey),Scharf, Manuel J.
-
-
Read Online
- Oxidation of fluoroalkyl alcohols using sodium hypochlorite pentahydrate [1]
-
Fluoroalkyl alcohols are effectivity oxidized to the corresponding fluoroalkyl carbonyl compounds by reaction with sodium hypochlorite pentahydrate in acetonitrile in the presence of acid and nitroxyl radical catalysts. Although the reaction proceeded slower under a nitroxyl radical catalyst- free condition, the desired carbonyl compounds were obtained in high yields. For the reaction with fluoroalkyl allylic alcohols, the corresponding α,β-epoxyketone hydrates were obtained in high yields.
- Kirihara, Masayuki,Suzuki, Katsuya,Nakakura, Kana,Saito, Katsuya,Nakamura, Riho,Tujimoto, Kazuki,Sakamoto, Yugo,Kikkawa, You,Shimazu, Hideo,Kimura, Yoshikazu
-
-
- Organometal-Free Arylation and Arylation/Trifluoroacetylation of Quinolines by Their Reaction with CF3-ynones and Base-Induced Rearrangement
-
The reaction of quinolines with CF3-ynones resulted in the formation of 1,3-oxazinoquinolines. Subsequent treatment of the reaction mixture with a base initiated deep structural transformation of primary products. Both steps proceed in very high yield. As a result, unusual rearrangement of 1,3-oxazinoquinolines to form either 2-arylquinolines or 2-aryl-3-trifluoroacetylquinolines was discovered. The decisive role of the base in the reaction direction was shown. Using these reactions, highly efficient pathways to 2-arylquinolines and 2-aryl-3-trifluoroacetylquinolines were elaborated to provide the corresponding compounds in high yields using a simple one-pot procedure. The possible mechanism of rearrangement is discussed.
- Muzalevskiy, Vasiliy M.,Belyaeva, Kseniya V.,Trofimov, Boris A.,Nenajdenko, Valentine G.
-
supporting information
p. 9993 - 10006
(2020/09/09)
-
- Copper-Mediated Deacylative Coupling of Ynones via C-C Bond Activation under Mild Conditions
-
The intermolecular deacylative coupling of unstrained ynones via C-C bond activation was accomplished by a CuCl-bpy system under mild reaction conditions. This protocol features facile cleavage of the C-C bond at room temperature, broad substrate scope, and efficient construction of important symmetric and unsymmetrical 1,3-diyne adducts through homo or cross coupling of ynones, respectively. The preliminary mechanistic investigations indicated that an acyl copper(III) complex is likely involved in this process.
- Feng, Lili,Hu, Tingjun,Zhang, Saisai,Xiong, Heng-Ying,Zhang, Guangwu
-
supporting information
p. 9487 - 9492
(2019/12/02)
-
- Catalytic Synthesis of Trifluoromethylated Allenes, Indenes, Chromenes, and Olefins from Propargylic Alcohols in HFIP
-
A general method to access CF3-substituted allenes from propargylic alcohols under Lewis acid catalysis in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as solvent is described. By tuning the reaction time and temperature, the obtained allenes rearr
- No?l, Florent,Vukovi?, Vuk D.,Yi, Jing,Richmond, Edward,Kravljanac, Pavle,Moran, Joseph
-
p. 15926 - 15947
(2019/12/25)
-
- Iridium-Catalyzed Asymmetric Transfer Hydrogenation of Alkynyl Ketones Using Sodium Formate and Ethanol as Hydrogen Sources
-
A green and efficient iridium-catalyzed asymmetric transfer hydrogenation of alkynyl ketones to chiral propargylic alcohols has been developed. By using sodium formate and ethanol as hydrogen sources, a series of alkynyl ketones were hydrogenated by chira
- Zhang, Yang-Ming,Yuan, Ming-Lei,Liu, Wei-Peng,Xie, Jian-Hua,Zhou, Qi-Lin
-
supporting information
p. 4486 - 4489
(2018/08/09)
-
- Pyrimidine as an Aryl C-H Activating Group
-
The Pd-catalyzed regioselective C-H activation/arylation, /iodination, and/acetoxylation reactions of 4-arylpyrimidines using aryl iodides, N-iodosuccinimide, and (diacetoxyiodo)benzene respectively as coupling partners are described. Suzuki-Miyaura coupl
- Gupta, Sahaj,Melanson, Jennifer A.,Vaillancourt, Louis,Nugent, William A.,Tanoury, Gerald J.,Schatte, Gabriele,Snieckus, Victor
-
supporting information
p. 3745 - 3748
(2018/07/22)
-
- Selective, Metal-Free Approach to 3- or 5-CF3-Pyrazoles: Solvent Switchable Reaction of CF3-Ynones with Hydrazines
-
A detailed study of the reaction of trifluoroacetylated acetylenes and aryl (alkyl) hydrazines was performed, aimed to the regioselective synthesis of 3- or 5-trifluoromethylated pyrazoles. It was found that the regioselectivity of reaction depends dramatically on the solvent nature. Highly polar protic solvents (hexafluoroisopropanol) favor the formation of 3-trifluoromethylpyrazoles. In contrast, when the reaction was performed in polar aprotic solvents (DMSO), the formation of their 5-CF3-substituted isomers was preferentially observed. Alternatively, the regioselective assembly of 3-CF3-substituted pyrazoles can be performed via two-step one-pot procedure. The reaction of trifluoromethylated ynones with aryl (alkyl) hydrazines in the presence of acidic catalysts leads to formation of the corresponding hydrazones. The latter can be smoothly transformed into 3-CF3-pyrazoles by treatment with a base. This solvent-switchable procedure was used for the preparation of such important drugs as Celebrex and SC-560 as well as their isomers in gram scale. The possible reaction mechanism is discussed.
- Muzalevskiy, Vasiliy M.,Rulev, Alexander Yu.,Romanov, Alexey R.,Kondrashov, Evgeniy V.,Ushakov, Igor A.,Chertkov, Vyacheslav A.,Nenajdenko, Valentine G.
-
p. 7200 - 7214
(2017/07/26)
-
- Solvent- and transition metal catalyst-dependent regioselectivity in the [3+2]cyclocondensation of trifluoromethyl-α,β-ynones with hydrazines: Switchable access to 3- and 5-trifluoromethylpyrazoles
-
The regioselectivity of the [3+2]cyclocondensation of trifluoromethyl-α,β-ynones with hydrazines can be readily tuned to preferentially afford either 3- or 5-trifluoromethylpyrazoles through variation of the reaction conditions. Under catalysis with copper(II) acetate (2.0 mol%), cyclocondensation proceeded smoothly to yield 3-trifluoromethylpyrazoles with high regioselectivity. In contrast, when the reaction was conducted in dimethyl sulfoxide under catalyst-free conditions, the formation of 5-trifluoromethylpyrazoles was predominantly observed.
- Hsieh, Min-Tsang,Kuo, Sheng-Chu,Lin, Hui-Chang
-
supporting information
p. 683 - 689
(2015/03/18)
-
- Copper-Catalyzed Trifluoromethylalkynylation of Isocyanides
-
The title reaction proceeds with acetylenic triflones and isocyanides under mild conditions using copper as a catalyst. This transformation provides an efficient access to (E)-N-alkyl trifluoromethyl alkynyl ketoimines, which are useful building blocks for the synthesis of CF3-containing N-heterocycles, propargylamines, etc.
- Lei, Jian,Wu, Xiaoxing,Zhu, Qiang
-
supporting information
p. 2322 - 2325
(2015/06/02)
-
- Bronsted acid catalyzed friedel-crafts alkylation reactions of trifluoromethyl-α,β-ynones with indoles
-
The successful development of a Bronsted acid catalyzed Friedel-Crafts alkylation reaction between trifluoromethyl-α,β-ynones and indoles has been described. The reaction is catalyzed by benzoic acid (5 mol%), with the indoles adding to the carbonyl carbon of the trifluoromethyl-α,β- ynones producing the corresponding 1,2-addition products as trifluoromethyl propargyl alcohols in high yields. Furthermore, treatment of the product with indoles in the presence of trifluoroacetic acid (10 mol%) afforded trifluoromethyl-functionalized unsymmetrical bis(indolyl)propynes in high yields.
- Sasaki, Shigeru,Ikekame, Yuta,Tanayama, Manabu,Yamauchi, Takayasu,Higashiyama, Kimio
-
supporting information
p. 2699 - 2703,5
(2012/12/12)
-
- A new entry for the oxidation of fluoroalkyl-substituted methanol derivatives: Scope and limitation of the organoiodine(V) reagent-catalyzed oxidation
-
Oxidation of various fluoroalkyl-substituted methanol derivatives under the influence of a catalytic amount of sodium 2-iodobenzenesulfonate and Oxone in CH3CN or CH3NO2 was investigated in detail. The efficiency of the newly developed oxidation was also evaluated by comparison to other oxidations, such as Dess-Martin, PDC, and Swern oxidation.
- Tanaka, Yusuke,Ishihara, Takashi,Konno, Tsutomu
-
experimental part
p. 99 - 104
(2012/05/07)
-
- Kinetic resolution of fluorinated propargyl alcohols by lipase-catalyzed enantioselective transesterification
-
In order to obtain optically active fluorinated propargyl alcohols, a lipase-catalyzed kinetic resolution has been carried out. The effect of lipase types, organic solvents, reaction temperature, and acyl donors was examined in the lipase-catalyzed transe
- Ko, Sung-Jin,Lim, Jung Yun,Jeon, Nan Young,Won, Keehoon,Ha, Deok-Chan,Kim, Bum Tae,Lee, Hyuk
-
experimental part
p. 1109 - 1114
(2009/09/30)
-
- 6,6-BICYCLIC RING SUBSTITUTED HETEROBICYCLIC PROTEIN KINASE INHIBITORS
-
Compounds of the formula (I) and pharmaceutically acceptable salts thereof, wherein XI, X2, X3, X4, X5, X6, X7, R1, and Q1 are defined herein, inhibit the IGF-1R enzyme and are useful for the treatment and/or prevention of hyperproliferative diseases such as cancer, inflammation, psoriasis, allergy/asthma, disease and conditions of the immune system, disease and conditions of the central nervous system.
- -
-
Page/Page column 429-430
(2008/06/13)
-
- PROCESSES FOR THE PREPARATION OF 1,5-DIARYLPYRAZOLES
-
Provided are processes for the preparation of the compound of the formula wherein R1, R3 and R4 are independently selected from the group consisting of hydrogen, halogen, hydroxyl, nitro, lower alkyl, lower alkoxy, carboxy, C1-C6 trihaloalkyl, and cyano, and R is amino or lower alkyl Also provided are synthetic intermediates that are useful as intermediates in the preparation of the compound of the formula 1.
- -
-
-
- Processes for the preparation of 1,5-diaryl-3-substituted-pyrazoles
-
Provided are processes and chemical intermediates useful for preparing a compound of the formula I wherein X is selected from the group consisting of C1-C6 trihalomethyl; C1-C6 alkyl; and an optionally substituted or di-substituted phenyl group of formula II: Y and Z are independently selected from the group consisting of substituted and unsubstiotuted aryl
- -
-
-
- Catalytic aerobic oxidative decarboxylation of α-trifluoromethyl-α-hydroxy acids to trifluoromethyl ketones
-
The oxidative decarboxylation of α-trifluoromethyl-α-hydroxy acids to trifluoromethyl ketones is carried out under mild catalytic aerobic conditions using a cobalt(III) complex in the presence of pivalaldehyde.
- Blay, Gonzalo,Fernández, Isabel,Marco-Aleixandre, Alicia,Monje, Belén,Pedro, José R,Ruiz, Rafael
-
p. 8565 - 8571
(2007/10/03)
-
- Reduction of metal-stabilized α-CF3-carbenium ion complexes under mild conditions: Synthesis, structures, and reactivity
-
Complexed α-CF3 propargyl alcohols of the general formula [(M2L6)(μ-η2,η2-RC?CCH(CF3)(OH))] were prepared with M2L6 = CO2(CO)6, R = CH3/sub
- Gruselle, Michel,Malezieux, Bernard,Andres, Roman,Amouri, Hani,Vaissermann, Jacqueline,Melikyan, Gagik G.
-
p. 359 - 368
(2007/10/03)
-
- Cesium fluoride catalyzed trifluoromethylation of esters, aldehydes, and ketones with (trifluoromethyl)trimethylsilane
-
The low reactivity of carboxylic esters toward (trifluoromethyl)trimethylsilane (TMS-CF3) was investigated. A universal cesium fluoride catalyzed procedure for nucleophilic trifluoromethylation was developed. At room temperature (25 °C, with catalytic amounts of cesium fluoride, carboxylic esters were found to react to give the silyl ether intermediates, which afforded the trifluoromethyl ketones after hydrolysis. Sulfonic, sulfinic, and selenic esters also show good reactivity, giving novel trifluoromethylated compounds. The trifluoromethylation method was also applied to aldehydes and ketones, which were transformed to trifluoromethyl silyl ether intermediates and afforded trifluoromethylated alcohols in excellent yields after acid hydrolysis. Ethylene glycol dimethyl ether was used as solvent for solid or high boiling substrates, and benzonitrile was used for the low boiling substrates.
- Singh, Rajendra P.,Cao, Ganfeng,Kirchmeier, Robert L.,Shreeve, Jean'ne M.
-
p. 2873 - 2876
(2007/10/03)
-
- Efficient large-scale synthesis of 4-phenyl-3-butyn-2-one, a key intermediate for a novel potent adenosine antagonist
-
Phenylacetylenic Grignard reagent reacts with acetic anhydride under mild conditions to give 4-phenyl-3-butyn-2-one in high yield. This method was applicable to a large-scale synthesis, and optimized reaction conditions have been investigated.
- Zanka, Atsuhiko
-
-
- Selective Reductions. 52. Efficient Asymmetric Reduction of α-Acetylenic α'-Fluoroalkyl Ketones with Either B-Chlorodiisopinocampheylborane or B-Isopinocampheyl-9-borabicyclononane in High Enantiomeric Purity. The Influence of Fluoro Groups in Such
-
A systematic study of the asymmetric reduction of prochiral α-acetylenic α'-fluoroalkyl ketones with (-)-B-chlorodiisopinocampheylborane and (-)-B-isopinocampheyl-9-borabicyclononane (R-Alpine-Borane, 2) reveals that perfluoro
- Ramachandran, P. Veeraraghavan,Gong, Baoqing,Teodorovic, Aleksandar V.,Brown, Herbert C.
-
p. 1061 - 1074
(2007/10/02)
-
- Oxidation of Fluoroalkyl-Substituted Carbinols by the Dess-Martin Reagent
-
The efficient oxidation of mono-, di-, tri-, and perfluoroalkyl-substituted carbinols has been accommplished by the Dess-Martin periodinane oxidant.A variety of functional groups are compatible with the oxidation procedure.Monitoring the oxidation by 19F NMR indicated that a discreet periodinane intermediate is formed during the course of the reaction.Nonnucleophilic or sterically encumbered α-thiofluoro carbinols were readily oxidized; however, a nucleophilic α-thio-substituted trifluoromethyl carbinol was not.A tert-butyl alcohol modified periodinane oxidant was ultimately employed to achieve oxidation in this example.
- Linderman, Russell J.,Graves, David M.
-
p. 661 - 668
(2007/10/02)
-
- Addition of Organocuprates to Acetylenic Di- and Trifluoromethyl Ketones. Regiospecific Synthesis of β,β-Disubstituted Unsaturated Fluoro ketones
-
A regiospecific synthesis of β,β-disubstituted-α,β-unsaturated di- and trifluoromethyl ketones has been achieved by the conjugate addition of higher order cyano cuprate reagents to acetylenic di- and trifluoromethyl ketones.An efficient and reproducible s
- Lindermann, Russel J.,Lonikar, Madhu S.
-
p. 6013 - 6022
(2007/10/02)
-
- AN EFFICIENT PROCEDURE FOR THE OXIDATION OF FLUORINATED CARBINOLS
-
The oxidation of di and trifluorocarbinols has been accomplished in high yields using the Dess-Martin periodane oxidant.
- Linderman, Russell J.,Graves, David M.
-
p. 4259 - 4262
(2007/10/02)
-
- REACTIVITY OF ORGANOTIN COMPOUNDS. XX. ACYLDEMETALLATION OF RSnMe3 compounds
-
The reactions of RSnMe3 with R=CH3 (I), C4H9 (II), C6H5 (III), 9-fluorenyl (IV), 9-methyl-9-fluorenyl (V), indenyl (VI), and C6H5CC (VII) with acetyl chloride (VIII), benzoyl chloride (IX), and trifluoroacetic anhydride (X) in methylene chloride at room temperature, leading to the formation of unsymmetrical ketones, were investigated.It was shown that the reactions of (I-III) with (VIII-X) and also of (VII) with (VIII) and (IX) only occur in the presence of aluminium chloride, whereas a catalyst is not required for the reactions of (VI) and (VII) with (X).Compounds(IV-VI) react with (VIII) and (IX) only in presence of Et4NCl or Bu4NBr, and this is explained by the participation of ion pairs R-+Sn(CH3)3, formed by coordination of the halide ion at the tin atom and possessing higher nucleophilicity than the covalent form RSn(CH3)3.The formation of 8-methyl-8-acetoxybenzofulvene in the reaction of (VI) with (VIII) shows that metallation of the strong CH acid 1-acetylindene by the action of compound (VI) occurs in the presence of a nucleophilic catalyst (Et4NCl).
- Kashin, A. N.,Bumagin, N. A.,Kalinovskii, I. O.,Beletskaya, I. P.,Reutov, O. A.
-
p. 1329 - 1334
(2007/10/02)
-
- A CONVENIENT SYNTHESIS OF ACETYLENIC KETONES FROM β-DIKETONES USING α,α-DIFLUOROALKYLAMINES AND FREEZE-DRIED POTASSIUM FLUORIDE
-
α,α-Difluoroalkylamines, such as 1-diethylamino-2-chloro-1,1,2-trifluoroethane (1) and 1-diethylamino-1,1,2,3,3,3-hexafluoropropane (2), were found to be useful dehydrating agents for the sysnthesis of acetylenic ketones from β-diketones in the presence o
- Kitazume, Tomoya,Ishikawa, Nobuo
-
p. 1327 - 1328
(2007/10/02)
-