- A simple procedure for nucleophilic perfluoroalkylation of organic and inorganic substrates
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The mixture RfI and tetrakis(dimethylamino)ethylene is used for the nucleophilic perfluoroalkylation. The reaction of chlorotrimethylsilane and RfI/tetrakis(dimethylamino)ethylene in diglyme results in the formation of RfSi(CH3)3 isolated in 55-81% yield. The interaction of this system with organic electrophiles such as benzoyl and benzensulphonyl chlorides, aliphatic and aromatic aldehydes and activated ketones leads to the formation of the corresponding condensation products in 24-62% yield.
- Petrov, Viacheslav A.
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- Sodium trifluoroacetate: An efficient precursor for the trifluoromethylation of aldehydes
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In a convenient and efficient procedure, the nucleophilic trifluoromethylation of aldehydes with sodium trifluoroacetate was achieved, using copper(I) halides as the catalyst.
- Chang, Ying,Cai, Chun
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- A chiral triaminosulfonium salt: Design and application to catalytic asymmetric synthesis
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The first chiral triaminosulfonium salt, tris((S,S)-3,4-diphenylpyrrolidino)sulfonium difluorotriphenylstannate, catalyzes trifluoromethylation of benzaldehyde with (trifluoromethyl)trimethylsilane to give the corresponding optically active alcohol with 52% ee.
- Kuroki, Yoshichika,Iseki, Katsuhiko
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- Fluoroform: An efficient precursor for the trifluoromethylation of aldehydes
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Fluoroform is shown to be an efficient trifluoromethylating agent when deprotonated using standard reagents in DMF. The important role of DMF in that reaction was demonstrated.
- Folleas, Benoit,Marek, Ilan,Normant, Jean-F,Jalmes, Laurent Saint
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- Lewis base-catalyzed perfluoroalkylation of carbonyl compounds and imines with (perfluoroalkyl)trimethylsilane
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Lewis base-catalyzed perfluoroalkylation of carbonyl compounds and aldimines with (perfluoroalkyl)trimethylsilanes (TMSCF3, TMSC 2F5, and TMSC3F7) is described. The nitrogen- or oxygen-containing anions generated from amides, imides, and carboxylic acids have been found to work as effective Lewis-base catalysts in perfluoroalkylation that proceeds via activation of the carbon-silicon bonds of (perfluoroalkyl)trimethylsilanes. Reactions of carbonyl compounds such as aldehydes, ketones, and esters with TMSCF3 in the presence of a catalytic amount of Lewis bases proceeded smoothly to afford the corresponding adducts in good-to-high yields under mild conditions. Although it was considered difficult, this catalytic perfluoroalkylation of various aldimines with (perfluoroalkyl)trimethylsilane in the presence of Lewis bases such as lithium acetate or benzoate proceeded efficiently to give the corresponding perfluoroalkylated adducts, because the aldimines here were weak electrophiles toward (perfluoroalkyl)trimethylsilanes. The present reaction is, therefore, the first example of a catalytic perfluoroalkylation of aldimines.
- Kawano, Yoshikazu,Kaneko, Nobuya,Mukaiyama, Teruaki
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- Organocatalysis approach to trifluoromethylation with fluoroform
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The organic base methodology exploits an access to generate the "trifluoromethyl anion" for carbonyl, ester, acid halide, epoxide, deuterium donor, and carbon dioxide substrates to afford the trifluoromethylation products with good overall efficiency even in organocatalysis conditions. The NMR analysis of the mixture of fluoroform and P4-base shows no change thereof. However, on addition of electrophiles, the trifluoromethylation products were obtained efficiently.
- Zhang, Yuan,Fujiu, Motohiro,Serizawa, Hiroki,Mikami, Koichi
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- Fluoroform: An efficient precursor for the trifluoromethylation of aldehydes
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Fluoroform is shown to be an efficient trifluoromethylating agent when deprotonated using standard reagents in DMF. The important role of DMF as a solvent but also as a reactant was demonstrated.
- Folléas, Beno?t,Marek, Ilan,Normant, Jean-F.,Saint-Jalmes, Laurent
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- BIARYL PYRAZOLES AS NRF2 REGULATORS
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The present invention relates to biaryl pyrazole compounds, methods of making them, pharmaceutical compositions containing them and their use as NRF2 regulators.
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Page/Page column 425; 426
(2017/08/01)
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- Chemo- and Enantioselective Addition and β-Hydrogen Transfer Reduction of Carbonyl Compounds with Diethylzinc Reagent in One Pot Catalyzed by a Single Chiral Organometallic Catalyst
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Using a single chiral phosphoramide-Zn(II) complex as the catalyst, the asymmetric β-H transfer reduction of aromatic α-trifluoromethyl ketones and enantioselective addition of aromatic aldehydes with Et2Zn in one pot were successfully realized, affording the corresponding additive products of secondary alcohols in high yields (up to 99%) with excellent enantioselectivities (up to 98% ee) and the reduction products of α-trifluoromethyl alcohols in good to excellent yields with up to 77% ee.
- Huang, Huayin,Zong, Hua,Bian, Guangling,Song, Ling
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p. 12614 - 12619
(2016/01/09)
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- Polyfluoroalkylation of carbonyl compounds by polyfluoroalkyl anions generated from polyfluorocarboxamides
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Polyfluoroalkyl anions, generated by reduction of (polyfluoroalkanoyl)piperidines with Et3BHK, were used for the polyfluoroalkylation of carbonyl compounds. Trifluoromethylation of aromatic aldehydes proceeded in good yields, and that of aliphatic aldehydes afforded a moderate yield. In contrast, the yield was low when the reaction involved benzophenone. Pentafluoroethylation and octafluorobutylation of aldehydes were also carried out by using the corresponding (polyfluoroalkanoyl)piperidines, which were prepared from commercially available polyfluorocompounds. The (polyfluoroalkanoyl)piperidines were also prepared through polyfluorination, and were used in the polyfluoroalkylation of aldehydes.
- Wakita, Natshumi,Hara, Shoji
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p. 1201 - 1212
(2016/11/07)
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- Nucleophilic trifluoromethylation with organoboron reagents
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Potassium trialkoxy(trifluoromethyl)borates are shown to behave as convenient reagents for nucleophilic trifluoromethylation of non-enolizable aldehydes and N-tosylimines to give CF3-substituted alcohols and N-tosylamines in good yields.
- Levin, Vitalij V.,Dilman, Alexander D.,Belyakov, Pavel A.,Struchkova, Marina I.,Tartakovsky, Vladimir A.
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supporting information; experimental part
p. 281 - 284
(2011/02/26)
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- METHODS OF TREATING SEROTONIN-MEDIATED DISEASES AND DISORDERS
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Methods are disclosed for treating serotonin-mediated diseases and disorders, which comprise inhibiting tryptophan hydroxylase (TPH) in patients in need thereof.
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- METHODS OF USING AND COMPOSITIONS COMPRISING TRYPTOPHAN HYDROXYLASE INHIBITORS
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Methods and compositions comprising tryptophan hydroxylase inhibitors are disclosed. Particular methods are directed at reducing or avoiding serotonin-mediated adverse effects associated with some drugs.
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- METHODS OF AFFECTING GASTROINTESTINAL TRANSIT AND GASTRIC EMPTYING, AND COMPOUNDS USEFUL THEREIN
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Methods and compounds are disclosed for affecting gastrointestinal motility and gastric emptying, which comprise inhibiting tryptophan hydroxylase (TPH) in patients in need thereof.
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- Multicyclic amino acid derivatives and methods of their use
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Compounds of formulae I and II are disclosed, as well as compositions comprising them and methods of their use to treat, prevent and manage serotonin-mediated diseases and disorders:
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Page/Page column 24
(2010/11/28)
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- Chemoselective reduction of ketones: Trifluoromethylketones versus methylketones
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Treatment of an equimolar mixture of trifluoromethylketones (TFMKs) and methylketones (MKs) with Et2Zn resulted in selective reduction of the TFMKs in good yield. In contrast, treatment of an equimolar mixture of TFMKs and MKs with NaBH4 in the presence of CeCl3 in EtOH/H 2O (10:1) at -10°C reduced only the MKs.
- Sasaki, Shigeru,Yamauchi, Takayasu,Kubo, Hajime,Kanai, Masatomi,Ishii, Akihiro,Higashiyama, Kimio
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p. 1497 - 1500
(2007/10/03)
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- N-heterocyclic carbene catalyzed trifluoromethylation of carbonyl compounds
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(Chemical Equation Presented) A novel N-heterocyclic carbene (NHC) catalyzed trifluoromethylation reaction of carbonyl compounds was discovered. Both enolizable and nonenolizable aldehydes and α-keto esters undergo facile trifluoromethylation with TMSCF3 at room temperature in the presence of only 0.5-1 mol % of the commercially available NHC (1), providing CF3-substituted alcohols in good yields. Selective trifluoromethylation of aldehydes over ketones can be achieved under NHC catalysis. These conditions are mild and simple and tolerate a variety of functional groups.
- Song, Jinhua J.,Tan, Zhulin,Reeves, Jonathan T.,Gallou, Fabrice,Yee, Nathan K.,Senanayake, Chris H.
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p. 2193 - 2196
(2007/10/03)
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- Nucleophilic trifluoromethylation using trifluoromethyl iodide. A new and simple alternative for the trifluoromethylation of aldehydes and ketones
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(Matrix Presented) A novel method for nucleophilic trifluoromethylation of aldehydes and ketones, based on photoinduced reduction of trifluoromethyl iodide by tetrakis(dimethylamino)ethylene (TDAE), is presented.
- Ait-Mohand, Samia,Takechi, Naoto,Medebielle, Maurice,Dolbier Jr., William R.
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p. 4271 - 4273
(2007/10/03)
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- Electroreductive coupling of halofluoro compounds with aldehydes
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Electroreductive intermolecular coupling of halofluoro compounds such as 1,1,1-trichloro-2,2,2-trifluoroethane, methyl chlorodifluoroacetate, and perfluoroalkyl halides with aldehydes took place effectively in the presence of chlorotrimethylsilane and one of the coupling products, 2,2-dichloro-3,3,3-trifluoro-1-phenyl-1-propranol, was selectively convertible to a variety of compounds with using the electroreduction as a key reaction.
- Shono,Kise,Oka
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p. 6567 - 6570
(2007/10/02)
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- Electroorganic Chemistry. 130. A Novel Trifluoromethylation of Aldehydes and Ketones Promoted by an Electrogenerated Base
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A base generated by the electroreduction of 2-pyrrolidone deprotonated trifluoromethane to form a trifluoromethyl anion equivalent.In the presence of hexamethyldisilazane, this species reacted with a variety of aldehydes and ketones to afford (trifluoromethyl)-carbinols in high yield.
- Shono, Tatsuya,Ishifune, Manabu,Okada, Toshio,Kashimura, Shigenori
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- Preparation of Trifluoromethyl and Other Perfluoroalkyl Compounds with (Perfluoroalkyl)trimethylsilanes
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The preparation of a variety of novel perfluoroalkyl-substituted compounds in high yields using easily prepared (perfluoroalkyl)trimethylsilanes (1a - c) is described. (Trifluoromethyl)-, (pentafluoroethyl)-, and (heptafluoropropyl)trimethylsilane, 1a - c, respectively, react readily with carbonyl compounds, such as aldehydes and ketones, by a fluoride-initiated catalytic process.Fluoride-initiated addition of 1 to a carbonyl group generates an oxyanionic species which then further catalyzes the reaction.Even enolizable carbonyl compounds react cleanly under the reaction conditions.A study of the scope of the reactivity of 1a toward other carbonyl groups in esters, lactones and an acid chloride was also carried out.Thus 1a reacts cleanly with five- and six-membered ring lactones.However, unactivated esters do not react under the reaction conditions.The acid chloride reacts with 1a to give a mixture of products.
- Krishnamurti, Ramesh,Bellew, Donald R.,Prakash, G. K. Surya
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p. 984 - 989
(2007/10/02)
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- Reactions of Trifluoromethyl Bromide and Related Halides: Part 9. Comparison between Additions to Carbonyl Compounds, Enamines, and Sulphur Dioxide in the Presence of Zinc
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A Barbier procedure, under moderate pressure, was used for the trifluoromethylation of various carbonyl compounds, starting from trifluoromethyl bromide and zinc in pyridine.Trifluoromethyl methanols were obtained from aldehydes and trifluoromethyl ketones from activated esters.Ethyl benzoate, or acetone, induced the formation of the solvated trifluoromethylzinc derivatives which did not react with carbonyl cpompounds.Consequently, the Barbier condensation in that case was considered to involve nascent organometallics reacting near the zinc surface.The reaction with sulphur dioxide, leading to trifluoromethanesulphinate, showed striking differences from that of carbonyl compounds.It was shown that the main pathway occcured in solution.This condensation was interpreted by the initial formation of sulphur dioxide radical anion, which reacts with trifluoromethyl bromide by a single-electron-transfer process.Attempts to condense iminium salts failed when a hydrogen atom was lacking in the α position.When the iminium ion can be transformed in situ to an enamine, a reaction occured, leading to α-trifluoromethyl ketones.This condensation was interpreted by a chain mechanism involving trifluoromethyl radicals.
- Tordeux, Marc,Francese, Catherine,Wakselman, Claude
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p. 1951 - 1957
(2007/10/02)
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- ELECTROCHEMICAL TRIFLUOROMETHYLATION OF CARBONYL COMPOUNDS
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The electroreduction of CF3Br in DMF containing aldehydes or ketones, using a sacrificial zinc anode, affords the corresponding trifluoromethyl alcohols together with the unreactive organozinc species CF3ZnBr and (CF3)2Zn.The alcohols are obtained with good yields from aldehydes.With ketones the organozinc species are formed preferentially to the alcohols, but the addition of tetramethylene-diamine allows the alcohols to form with moderate yields.
- Sibille, S.,Mcharek, S.,Perichon, J.
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p. 1423 - 1428
(2007/10/02)
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- Oxidation of Fluoroalkyl-Substituted Carbinols by the Dess-Martin Reagent
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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.
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p. 661 - 668
(2007/10/02)
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