3108-32-5Relevant academic research and scientific papers
Electrochemical synthesis and structural characterisation of cadmium and mercury complexes containing pyrimidine-2-thionate ligands
Rodriguez, Antonio,Sousa-Pedrares, Antonio,Garcia-Vazquez, Jose A.,Romero, Jaime,Sousa, Antonio
, p. 2242 - 2254 (2005)
The electrochemical oxidation of anodic metal (cadmium or mercury) in a cell containing an acetonitrile solution of the appropriate pyrimidine-2-thione (RpymSH) affords complexes [M(RpymS)2] (M = Cd, Hg; R = 4-CF 3, 4,6-CF3,Me and 4,6-CF3,Ph). When 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen) was added to the electrolytic cell, adducts of cadmium and compounds with these coligands were obtained. All the compounds have been characterised by microanalysis, IR spectroscopy and, in the case of the compounds that were sufficiently soluble, by 1H, 13C and 199Hg NMR spectroscopy. The compounds [Cd(4-CF3pymS)2] (1), [Cd(4,6-CF 3MepymS)2(bipy)] (4), [Cd(4,6-CF3PhpymS) 2 (phen)] (6) and [Hg(4,6-CF3MepymS)2] (8) were also characterised by X-ray diffraction. Compound 1 presents a polymeric structure with the polymer chains interconnected by intermolecular C-H...N interactions. Compounds 4 and 6 adopt mononuclear structures, with weak inter- and intra-molecular C-H...π interactions, as well as π-π stacking interactions for compound 6. Compound 8 also presents a mononuclear structure with intermolecular π-π interactions between the pyrimidine rings and additional weak Hg...Hg contacts (3.484 A). Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
HETEROCYCLIC COMPOUNDS AS ANTI-VIRAL AGENTS
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Page/Page column 47, (2021/07/31)
The present invention discloses compounds of Formula (I), or pharmaceutically acceptable salts, esters, or prodrugs thereof: which inhibit Respiratory Syncytial Virus (RSV) or HMPV. The present invention further relates to pharmaceutical compositions comp
Radical Trifluoroacetylation of Alkenes Triggered by a Visible-Light-Promoted C–O Bond Fragmentation of Trifluoroacetic Anhydride
Jeschke, Gunnar,Katayev, Dmitry,N?tel, Nicolas Yannick,Rombach, David,Zhang, Kun
supporting information, p. 22487 - 22495 (2021/09/09)
We report a mild and operationally simple trifluoroacylation strategy of olefines, that utilizes trifluoroacetic anhydride as a low-cost and readily available reagent. This light-mediated process is fundamentally different from conventional methodologies and occurs through a trifluoroacyl radical mechanism promoted by a photocatalyst, which triggers a C?O bond fragmentation. Mechanistic studies (kinetic isotope effects, spectroelectrochemistry, optical spectroscopy, theoretical investigations) highlight the evidence of a fleeting CF3CO radical under photoredox conditions. The trifluoroacyl radical can be stabilized under CO atmosphere, delivering the trifluoroacetylation product with higher chemical efficiency. Furthermore, the method can be turned into a trifluoromethylation protocol by simply changing the reaction parameters. Beyond simple alkenes, this method allows for chemo- and regioselective functionalization of small-molecule drugs and common pharmacophores.
Synthesis of trifluoromethyl ketones by nucleophilic trifluoromethylation of esters under a fluoroform/KHMDS/triglyme system
Fujihira, Yamato,Liang, Yumeng,Ono, Makoto,Hirano, Kazuki,Kagawa, Takumi,Shibata, Norio
supporting information, p. 431 - 438 (2021/03/20)
A straightforward method that enables the formation of biologically attractive trifluoromethyl ketones from readily available methyl esters using the potent greenhouse gas fluoroform (HCF3, HFC-23) was developed. The combination of fluoroform and KHMDS in triglyme at ?40 °C was effective for this transformation, with good yields as high as 92%. Substrate scope of the trifluoromethylation procedure was explored for aromatic, aliphatic, and conjugated methyl esters. This study presents a straightforward trifluoromethylation process of various methyl esters that convert well to the corresponding trifluoromethyl ketones. The tolerance of various pharmacophores under the reaction conditions was also explored.
The Importance of 1,5-Oxygen???Chalcogen Interactions in Enantioselective Isochalcogenourea Catalysis
Cockroft, Scott L.,Elmi, Alex,Frost, Aileen B.,Ling, Kenneth B.,McLaughlin, Calum,Morris, Rylie K.,Pascoe, Dominic J.,Slawin, Alexandra M. Z.,Smith, Andrew D.,Smith, Terry K.,Willoughby, Patrick H.,Woods, Andrew M.,Young, Claire M.,de la Houpliere, Alix
supporting information, p. 3705 - 3710 (2020/02/11)
The importance of 1,5-O???chalcogen (Ch) interactions in isochalcogenourea catalysis (Ch=O, S, Se) is investigated. Conformational analyses of N-acyl isochalcogenouronium species and comparison with kinetic data demonstrate the significance of 1,5-O???Ch interactions in enantioselective catalysis. Importantly, the selenium analogue demonstrates enhanced rate and selectivity profiles across a range of reaction processes including nitronate conjugate addition and formal [4+2] cycloadditions. A gram-scale synthesis of the most active selenium analogue was developed using a previously unreported seleno-Hugerschoff reaction, allowing the challenging kinetic resolutions of tertiary alcohols to be performed at 500 ppm catalyst loading. Density functional theory (DFT) and natural bond orbital (NBO) calculations support the role of orbital delocalization (occurring by intramolecular chalcogen bonding) in determining the conformation, equilibrium population, and reactivity of N-acylated intermediates.
Oxidation of 4-Aryl-1,1,1-trifluorobut-2-en-2-yl Trifluoro?-methanesulfonates by 4-Picoline-N-Oxide: A Novel Approach to β-Trifluoromethyl-α,β-enones
Li, Dong,Lv, Shujun,Qu, Jingping,Zhou, Yuhan
, p. 1203 - 1210 (2020/04/15)
An efficient approach to β-trifluoromethyl-α,β-enones via oxidation of 4-aryl-1,1,1-trifluorobut-2-en-2-yl trifluoromethanesulfonates is described. The reaction proceeds smoothly under mild and metal?-free conditions and tolerates a wide range of functional groups. Various β-trifluoromethyl-α,β-enones were obtained in moderate to good yields.
Evaluating aryl esters as bench-stable C(1)-ammonium enolate precursors in catalytic, enantioselective Michael addition-lactonisations
Young, Claire M.,Taylor, James E.,Smith, Andrew D.
supporting information, p. 4747 - 4752 (2019/05/24)
An evaluation of a range of aryl, alkyl and vinyl esters as prospective C(1)-ammonium enolate precursors in enantioselective Michael addition-lactonisation processes with (E)-trifluoromethylenones using isothiourea catalysis is reported. Electron deficient aryl esters are required for reactivity, with 2,4,6-trichlorophenyl esters providing optimal product yields. Catalyst screening showed that tetramisole was the most effective isothiourea catalyst, giving the desired dihydropyranone product in excellent yield and stereoselectivity (up to 90 : 10 dr and 98 : 2 er). The scope and limitations of this process have been evaluated, with a range of diester products being generated after ring-opening with MeOH to give stereodefined dihydropyranones with excellent stereocontrol (10 examples, typically ～90 : 10 dr and >95 : 5 er).
One-Pot Catalytic Enantioselective Synthesis of 2-Pyrazolines
Thomson, Connor J.,Barber, David M.,Dixon, Darren J.
supporting information, p. 2469 - 2473 (2019/02/01)
A scalable, one-pot, enantioselective catalytic synthesis of 2-pyrazolines from beta-substituted enones and hydrazines is described. Pivoting on a two-stage catalytic Michael addition/condensation strategy, the use of an aldehyde to generate a suitable hydrazone derivative of the hydrazine was found to be key for curtailing background reactivity and tuning the catalyst-controlled enantioselectivity. The new synthetic method is easy to perform, uses a new and readily prepared cinchona-derived bifunctional catalyst, is broad in scope, and tolerates a range of functionalities with high enantioselectivity (up to >99:1 e.r.). The significant scalability of this methodology was demonstrated with the synthesis of more than 80 grams of a pyrazoline product with 89 % catalyst recovery.
One-Pot Sequential Multistep Transformation of α,β-Unsaturated Trifluoromethyl Ketones: Facile Synthesis of Trifluoromethylated 2-Pyridones
Lv, Ning,Tian, Yi-Qiang,Zhang, Fa-Guang,Ma, Jun-An
supporting information, p. 605 - 609 (2019/03/07)
A one-pot transformation of α,β-unsaturated trifluoromethyl ketones with 2-(phenylsulfinyl)acetamide to give trifluoromethylated 2-pyridones is realized. The reaction proceeds under mild conditions and involves multiple steps in an expeditious and controlled sequence to provide efficient access to a broad range of trifluoromethylated 2-pyridones in moderate to high yields. Moreover, further synthetic manipulations permit the routine synthesis of a diverse array of trifluoromethylated pyridines with good efficiency.
A Remarkable Influence of a Trifluoromethyl Group on the Reactions of β-Mercaptoalcohols with Fluorinated α-Bromoenones
Obijalska, Emilia,Pawelec, Maria,Mlostoń, Grzegorz,Capperucci, Antonella,Tanini, Damiano,Heimgartner, Heinz
, p. 3716 - 3723 (2018/04/09)
Isomeric fluorinated α-bromoenones react with dinucleophilic β-mercaptoalcohols in CH2Cl2 at room temperature in the presence of Et3N in a multistep process. Depending on the position of the CF3 group, different O,S-heterocycles or non-cyclic products were obtained. With 3-bromo-1,1,1-trifluorobut-3-en-2-ones derivatives of 1,4-oxathianes were formed, but isomeric 2-bromo-4,4,4-trifluorobut-2-en-1-ones yielded 1,3-oxathiolanes or non-cyclic sulfides. The thia-Michael addition is proposed as the initial step of the reaction, and the final heterocyclization is governed by the location of the CF3 group.
