- 2-Azetidinone cholesterol absorption inhibitors: Structure-activity relationships on the heterocyclic nucleus
-
A series of azetidinone cholesterol absorption inhibitors related to SCH 48461 ((-)-6) has been prepared, and compounds were evaluated for their ability to inhibit hepatic cholesteryl ester formation in a cholesterol-fed hamster model. Although originally
- Clader, John W.,Burnett, Duane A.,Caplen, Mary Ann,Domalski, Martin S.,Dugar, Sundeep,Vaccaro, Wayne,Sher, Rosy,Browne, Margaret E.,Zhao, Hongrong,Burrier, Robert E.,Salisbury, Brian,Davis Jr., Harry R.
-
-
Read Online
- Direct Addition of Grignard Reagents to Aliphatic Carboxylic Acids Enabled by Bulky turbo-Organomagnesium Anilides
-
The synthesis of ketones through addition of organometallic reagents to aliphatic carboxylic acids is a straightforward strategy that is limited to organolithium reagents. More desirable Grignard reagents can be activated and controlled with a bulky aniline-derived turbo-Hauser base. This operationally simple procedure allows the straightforward preparation of a variety of aliphatic and perfluoroalkyl ketones alike from functionalized alkyl, aryl and heteroaryl Grignard reagents.
- Colas, Kilian,Kohlhepp, Stefanie V.,Mendoza, Abraham,V. D. dos Santos, A. Catarina
-
supporting information
(2022/02/02)
-
- 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
-
-
- Direct Synthesis of Tri-/Difluoromethyl Ketones from Carboxylic Acids by Cross-Coupling with Acyloxyphosphonium Ions
-
A simple and straightforward approach to the synthesis of trifluoromethyl and difluoromethyl ketones from widely available carboxylic acids is disclosed. The transformation utilizes an acyloxyphosphonium ion as the active electrophile, conveniently generated in situ from the carboxylic acid substrate by using commodity chemicals. The utility of the reaction system is exemplified by its chemoselectivity, with tolerance to a variety of important functional groups. The late-stage functionalization of carboxylic acid active pharmaceutical ingredients and pharmaceutically relevant compounds is also discussed.
- Ispizua-Rodriguez, Xanath,Munoz, Socrates B.,Krishnamurti, Vinayak,Mathew, Thomas,Prakash
-
supporting information
p. 15908 - 15913
(2021/10/07)
-
- Trifluoromethylation of Benzoic Acids: An Access to Aryl Trifluoromethyl Ketones
-
The trifluoromethylation of benzoic acids with TMSCF3 was achieved through nucleophilic substitution with the use of anhydrides as an in situ activating reagent. Under the reaction conditions, a wide range of carboxylic acids including the bioactive ones worked well, thus providing a facile and efficient method for preparing aryl trifluoromethyl ketones from the readily available starting materials.
- Liu, Xue,Liu, Long,Huang, Tianzeng,Zhang, Jingjing,Tang, Zhi,Li, Chunya,Chen, Tieqiao
-
supporting information
p. 4930 - 4934
(2021/06/30)
-
- Synthesis of trifluoromethyl ketones by nucleophilic trifluoromethylation of esters under a fluoroform/KHMDS/triglyme system
-
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.
- Fujihira, Yamato,Liang, Yumeng,Ono, Makoto,Hirano, Kazuki,Kagawa, Takumi,Shibata, Norio
-
supporting information
p. 431 - 438
(2021/03/20)
-
- Access to Aryl and Heteroaryl Trifluoromethyl Ketones from Aryl Bromides and Fluorosulfates with Stoichiometric CO
-
We report a sequential one-pot preparation of aromatic trifluoromethyl ketones starting from readily accessible aryl bromides and fluorosulfates, the latter easily prepared from the corresponding phenols. The methodology utilizes low pressure carbon monoxide generated ex situ from COgen to generate Weinreb amides as reactive intermediates that undergo monotrifluoromethylation affording the corresponding aromatic trifluoromethyl ketones (TFMKs) in good yields. The stoichiometric use of CO enables the possibility for accessing 13C-isotopically labeled TFMK by switching to the use of 13COgen.
- Johansen, Martin B.,Gedde, Oliver R.,Mayer, Thea S.,Skrydstrup, Troels
-
p. 4068 - 4072
(2020/06/03)
-
- A Hammett Study of Clostridium acetobutylicum Alcohol Dehydrogenase (CaADH): An Enzyme with Remarkable Substrate Promiscuity and Utility for Organic Synthesis
-
Described is a physical organic study of the reduction of three sets of carbonyl compounds by the NADPH-dependent enzyme Clostridium acetobutylicum alcohol dehydrogenase (CaADH). Previous studies in our group have shown this enzyme to display broad substrate promiscuity, yet remarkable stereochemical fidelity, in the reduction of carbonyl compounds, including α-, β- and γ-keto esters (d -stereochemistry), as well as α,α-difluorinated-β-keto phosphonate esters (l -stereochemistry). To better mechanistically characterize this promising dehydrogenase enzyme, we report here the results of a Hammett linear free-energy relationship (LFER) study across three distinct classes of carbonyl substrates; namely aryl aldehydes, aryl β-keto esters and aryl trifluoromethyl ketones. Rates are measured by monitoring the decrease in NADPH fluorescence at 460 nm with time across a range of substrate concentrations for each member of each carbonyl compound class. The resulting v 0 versus [S] data are subjected to least-squares hyperbolic fitting to the Michaelis-Menton equation. Hammett plots of log(V max) versus σ X yield the following Hammett parameters: (i) for p -substituted aldehydes, ρ = 0.99 ± 0.10, ρ = 0.40 ± 0.09; two domains observed, (ii) for p -substituted β-keto esters ρ = 1.02 ± 0.31, and (iii) for p -substituted aryl trifluoromethyl ketones ρ = -0.97 ± 0.12. The positive sign of ρ indicated for the first two compound classes suggests that the hydride transfer from the nicotinamide cofactor is at least partially rate-limiting, whereas the negative sign of ρ for the aryl trifluoromethyl ketone class suggests that dehydration of the ketone hydrate may be rate-limiting for this compound class. Consistent with this notion, examination of the 13 C NMR spectra for the set of p -substituted aryl trifluo romethyl ketones in 2percent aqueous DMSO reveals significant formation of the hydrate (gem -diol) for this compound family, with compounds bearing the more electron-withdrawing groups showing greater degrees of hydration. This work also presents the first examples of the CaADH-mediated reduction of aryl trifluoromethyl ketones, and chiral HPLC analysis indicates that the parent compound α,α,α-trifluoroacetophenone is enzymatically reduced in 99percent ee and 95percent yield, providing the (S)-stereoisomer, suggesting yet another compound class for which this enzyme displays high enantioselectivity.
- Berkowitz, David B.,Kudalkar, Gaurav P.,Lee, Joshua D.,Tiwari, Virendra K.
-
supporting information
p. 237 - 247
(2020/02/18)
-
- NiH-Catalyzed Migratory Defluorinative Olefin Cross-Coupling: Trifluoromethyl-Substituted Alkenes as Acceptor Olefins to Form gem-Difluoroalkenes
-
We report a NiH-catalyzed migratory defluorinative coupling between two electronically differentiated olefins. A broad range of unactivated donor olefins can be joined directly to acceptor olefins containing an electron-deficient trifluoromethyl substituent in both intra- and intermolecular fashion to form gem-difluoroalkenes. This migratory coupling shows both site- and chemoselectivity under mild conditions, with the formation of a tertiary or quaternary carbon center.
- Chen, Fenglin,He, Yuli,Huang, Genping,Xu, Xianfeng,Zhu, Shaolin
-
supporting information
p. 5398 - 5402
(2020/02/28)
-
- REACTIVE EXTRACTION OF WATER
-
Described herein are methods and compounds for extracting water from an aqueous solution. For example, some embodiments include method for extracting water from an aqueous solution, comprising contacting the aqueous solution with a compound comprising one or more carbonyl moieties having an equilibrium constant for a hydration of the carbonyl moiety of at least about 0.5; separating a composition comprising the hydrated compound from the aqueous solution; and reacting the hydrated compound to obtain water.
- -
-
Paragraph 0073-0076
(2020/04/09)
-
- Construction of trifluoromethylated quaternary stereocenters: Via p -quinone methides
-
Development of a new synthetic method for the construction of quaternary centers with a trifluoromethyl group was realized by way of 1,6-addition of various nucleophiles including active methylene compounds to highly reactive δ-trifluoromethylated p-quinone methides generated in situ from the corresponding tertiary carbonates with a catalytic amount of an appropriate base.
- Terashima, Kyu,Kawasaki-Takasuka, Tomoko,Agou, Tomohiro,Kubota, Toshio,Yamazaki, Takashi
-
supporting information
p. 3031 - 3034
(2020/03/19)
-
- Selective Acylation of Aryl- A nd Heteroarylmagnesium Reagents with Esters in Continuous Flow
-
A selective acylation of readily accessible organomagnesium reagents with commercially available esters proceeds at convenient temperatures and short residence times in continuous flow. Flow conditions allow us to prevent premature collapse of the hemiacetal intermediates despite noncryogenic conditions, thus furnishing ketones in good yields. Throughout, the coordinating ability of the ester and/or Grignard was crucial for the reaction outcome. This was leveraged by the obtention of several bisaryl ketones using 2-hydroxy ester derivatives as substrates.
- Heinz, Benjamin,Djukanovic, Dimitrije,Ganiek, Maximilian A.,Martin, Benjamin,Schenkel, Berthold,Knochel, Paul
-
supporting information
p. 493 - 496
(2020/01/31)
-
- Palladium-catalyzed fluoroacylation of (Hetero)arylboronic acid with fluorothioacetates at ambient temperature
-
A palladium-catalyzed fluoroacylation of (hetero)aryl boronic acid with the fluorothioacetates is described at ambient temperature. A variety of aryl, and heteroaryl boronic acids are compatible in the reaction, affording the corresponding fluoroalkyl ketones in moderate to good yields. Further late-stage di-, and trifluoroacylation of drug molecule clofibrate and estrone demonstrated the synthetic practicability of this protocol.2009 Elsevier Ltd. All rights reserved.
- Ban, Shu-Rong,Cao, Ya-Fang,Dai, Hui-Xiong,Wang, Xing,Xu, Hui,Yi, Xing
-
supporting information
(2020/03/23)
-
- Catalytic Oxidation of Alcohols Using a 2,2,6,6-Tetramethylpiperidine-N-hydroxyammonium Cation
-
The oxidation of alcohols to aldehydes, ketones, and carboxylic acids is reported using 2,2,6,6-tetramethylpiperidine-4-acetamido-hydroxyammonium tetrafluoroborate as a catalyst in conjunction with sodium hypochlorite pentahydrate as a terminal oxidant. The reaction is generally complete within 30–120 min using an acetonitrile/water mix as the solvent, and no additives are required. Product yields are good to excellent and of particular note is that the methodology can be used to access aryl α-trifluoromethyl ketones.
- Miller, Shelli A.,Bisset, Kathryn A.,Leadbeater, Nicholas E.,Eddy, Nicholas A.
-
supporting information
p. 1413 - 1417
(2019/01/04)
-
- Oxidation of α-trifluoromethyl and non-fluorinated alcohols: Via the merger of oxoammonium cations and photoredox catalysis
-
We present an alcohol oxidation strategy to access α-trifluoromethyl ketones (TFMKs) merging catalytic oxoammonium cation oxidation with visible-light photoredox catalysis. This work uses 4-acetamido-(2,2,6,6-tetramethyl-piperidin-1-yl)oxyl as an organic oxidant capable of generating TFMKs in good yields. The methodology serves as an improvement over previous reports of an analogous oxidation strategy requiring superstoichiometric quantities of oxidant. Both primary and secondary non-fluorinated alcohols can also be oxidised in good yields.
- Pistritto, Vincent A.,Paolillo, Joshua M.,Bisset, Kathryn A.,Leadbeater, Nicholas E.
-
supporting information
p. 4715 - 4719
(2018/07/06)
-
- Radical C(sp2)-H Trifluoromethylation of Aldehydes in Aqueous Solution
-
The copper-mediated C(sp2)-H trifluoromethylation of aldehydes is described. The reaction of aldehydes with (bpy)Cu(CF3)3, Et3SiH, and K2S2O8 in aqueous acetone at room temperatu
- Zhang, Pei,Shen, Haigen,Zhu, Lin,Cao, Weiguo,Li, Chaozhong
-
supporting information
p. 7062 - 7065
(2018/11/21)
-
- Spatiotemporal Control of Pre-existing Alkene Geometry: A Bio-Inspired Route to 4-Trifluoromethyl-2H-chromenes
-
Routes to prepare C4-trifluoromethyl analogues of the 2H-chromene scaffold are scarce: this is particularly striking given the importance of fluorine in pharmaceutical development. To address this limitation, a facile strategy has been developed that is reliant on catalytic, geometric isomerization of easily accessible allylic alcohols (up to >95:5) followed by intramolecular cyclization via Pd catalysis (up to 96%). This concise biomimetic approach emulates the photoisomerization/cyclization cascade inherent to phenylpropanoid biosynthesis.
- Fa?bender, Svenja I.,Metternich, Jan B.,Gilmour, Ryan
-
supporting information
p. 724 - 727
(2018/02/09)
-
- Enantioselective Synthesis of Trifluoromethyl α,β-Unsaturated δ-Lactones via Vinylogous Aldol-Lactonization Cascade
-
The novel vinylogous aldol-lactonization cascade of alkylidene oxindole with trifluoromethyl ketones is presented. The reaction, catalyzed by a bifunctional tertiary amine, provides an efficient application of the vinylogous reactivity of alkylidene oxindoles for the preparation of enantioenriched trifluoromethylated α,β-unsaturated δ-lactones.
- Crotti, Simone,Di Iorio, Nicola,Mazzanti, Andrea,Righi, Paolo,Bencivenni, Giorgio
-
p. 12440 - 12448
(2018/10/09)
-
- Facile diversification of simple benzo[b]thiophenes via thienobenzyne intermediates
-
Thienobenzynes, which are thiophene-fused novel benzyne species, are efficiently generated via an iodine-magnesium exchange reaction of ortho-iodoaryl triflate-type precursors using a silylmethyl Grignard reagent as the activator. The method allows for facile preparation of a diverse range of multisubstituted benzothiophenes from readily available simple benzothiophenes.
- Morita, Takamoto,Yoshida, Suguru,Kondo, Masakazu,Matsushita, Takeshi,Hosoya, Takamitsu
-
supporting information
p. 81 - 84
(2017/02/10)
-
- MgCl2-catalyzed trifluoromethylation of carbonyl compounds using (trifluoromethyl)trimethylsilane as the trifluoromethylating agent
-
Using (trifluoromethyl)trimethylsilane (TMSCF3) as the trifluoromethylating agent, MgCl2-catalyzed trifluoromethylation of carbonyl compounds proceeded readily at room temperature. In the presence of 10 mol% of MgCl2, a variety of carbonyl substrates such as aliphatic/aromatic aldehydes, acyclic/cyclic ketones and esters could be trifluoromethylated in DMF, giving the corresponding trimethylsilyl ethers (ketals) in up to 93% isolated yields. Trifluoromethylketones could be readily obtained after hydrolysis of the trimethylsilyl ketals. The reactions could tolerate air and moisture, and the use of oxygen and moisture-free conditions was not required.
- Cui, Bin,Sun, Hui,Xu, Yibo,Duan, Lili,Li, Yue-Ming
-
p. 6754 - 6762
(2017/11/09)
-
- Asymmetric Construction of Pyrrolidines Bearing a Trifluoromethylated Quaternary Stereogenic Center via CuI-Catalyzed 1,3-Dipolar Cycloaddition of Azomethine Ylides with β-CF3-β,β-Disubstituted Nitroalkenes
-
A direct and convenient method has been developed for the synthesis of optically active pyrrolidines bearing a quaternary stereogenic center containing a CF3 group at the C-3 position of the pyrrolidine ring. The synthesis system, CuI/Si-FOXAP-catalyzed exo-selective 1,3-dipolar cycloaddition of azomethine ylides with β-CF3-β,β-disubstituted nitroalkenes, provides pyrrolidines with high diastereoselectivities (up to >98:2 d.r.) and excellent enantioselectivities (up to >99.9 ee) and performs well for a broad scope of substrates under mild conditions.
- Tang, Li-Wei,Zhao, Bao-Jing,Dai, Li,Zhang, Man,Zhou, Zhi-Ming
-
supporting information
p. 2470 - 2477
(2016/09/13)
-
- Copper-Mediated Trifluoroacetylation of Arenediazonium Salts with Ethyl Trifluoropyruvate
-
A copper-mediated trifluoroacetylation of various arenediazonium salts with ethyl trifluoropyruvate is reported. The reaction proceeded smoothly under mild conditions at room temperature giving trifluoromethyl aryl ketones in moderate to good yields. A variety of functional groups, including methoxy, hydroxy, ester, ketone, trifluoromethyl, and halide groups, were well tolerated. A possible reaction mechanism involving an aryl radical intermediate was proposed and supported by experimental evidence. This reaction provides a new route to trifluoromethyl aryl ketones, notable synthetic targets, from the corresponding anilines.
- Wu, Wei,Tian, Qinli,Chen, Taotao,Weng, Zhiqiang
-
supporting information
p. 16455 - 16458
(2016/11/11)
-
- Palladium-catalyzed carbonylative coupling of aryl iodides with an organocopper reagent: A straightforward procedure for the synthesis of aryl trifluoromethyl ketones
-
A palladium-catalyzed carbonylative coupling of aryl iodides with a (trifluoromethyl)copper reagent has been developed. A wide range of substrates have been transformed into their corresponding trifluoromethyl ketones in good to excellent yields under mild conditions with high efficiency and excellent functional-group compatibility. Preliminary mechanistic investigations suggest that the transmetallation of an acylpalladium intermediate with the (trifluoromethyl)copper reagent seems to be involved in the catalytic cycle. Notably, this report represents one of the few studies on carbonylative coupling with organocopper reagents.
- Zhu, Fengxiang,Yang, Guangfu,Zhou, Shaolin,Wu, Xiao-Feng
-
p. 57070 - 57074
(2016/07/07)
-
- High-Pressure-Mediated Asymmetric Organocatalytic Hydroxyalkylation of Indoles with Trifluoromethyl Ketones
-
An enantioselective hydroxyalkylation of indoles and 7-azaindole with trifluoromethyl ketones was found to be effectively promoted under high-pressure conditions with a low loading of Cinchona alkaloids (e.g., 1–3 mol% of cinchonidine). Chiral tertiary alcohols containing a trifluoromethyl group were obtained at 9 kbar with good yield and enantioselectivity up to 89%, whereas usually merely traces of products were detected at atmospheric pressure. (Figure presented.).
- Kasztelan, Adrian,Biedrzycki, Micha?,Kwiatkowski, Piotr
-
supporting information
p. 2962 - 2969
(2016/09/16)
-
- Organocatalytic Aerobic Oxidation of α-Fluoroalkyl Alcohols to Fluoroalkyl Ketones at Room Temperature
-
The organocatalytic aerobic oxidation of electron-deficient α-fluoroalkyl alcohols at room temperature is described. The resulting fluoroalkyl ketones are versatile synthetic intermediates for a variety of fluorine-containing molecules. This otherwise difficult transformation has now been accomplished by the reaction of α-fluoroalkyl alcohols with N-oxyl radicals, catalytically generated from 9-azabicyclo[3.3.1]nonan-3-one N-oxyl/nitrogen oxide (keto-ABNO/NOx) and oxygen in acetic acid (AcOH), affording the corresponding fluoroalkyl ketones in high yield. This operationally simple reaction can be performed under mild conditions, and was applied to a wide range of alcohols (20 examples), thus demonstrating a high functional group tolerance. Moreover, a modified one-pot protocol based on this method was able to convert an aldehyde to a trifluoromethyl ketone on a gram scale.
- Kadoh, Yoichi,Tashiro, Masayuki,Oisaki, Kounosuke,Kanai, Motomu
-
p. 2193 - 2198
(2015/07/27)
-
- Catalytic highly enantioselective transfer hydrogenation of β-trifluoromethyl nitroalkenes. An easy and general entry to optically active β-trifluoromethyl amines
-
In the presence of a thiourea catalyst, β-CF3 nitroalkenes react with Hantzsch esters in a highly enantioselective fashion, giving a broad range of β-CF3 amine precursors with a tertiary stereocentre at the β-position. This reaction
- Martinelli, Emilie,Vicini, Anna Chiara,Mancinelli, Michele,Mazzanti, Andrea,Zani, Paolo,Bernardi, Luca,Fochi, Mariafrancesca
-
supporting information
p. 658 - 660
(2015/01/09)
-
- One-pot multistep synthesis of trisubstituted alkenes from N -tosylhydrazones and alcohols
-
A one-pot procedure for the synthesis of trisubstituted alkenes from N-tosylhydrazones and alcohols is reported. This procedure combines the aerobic oxidation reaction and Wittig reaction in one pot, which avoids using of environmentally toxic oxidants and isolation of the intermediates. The simple procedure makes it very attractive for the synthesis of trisubstituted alkenes when alcohols are used as starting materials. A variety of trisubstituted alkenes as well as trifluoromethyl-substituted alkenes were obtained in moderate to good yields (up to 84%) with good E-selectivity (up to 99%). Georg Thieme Verlag Stuttgart.New York.
- Sha, Qiang,Wei, Yunyang
-
supporting information
p. 2353 - 2361
(2014/11/08)
-
- Diversity-oriented approach to CF3CHF-, CF3CFBr-, CF3CF2-, (CF3)2CH-, and CF3(SCF3)CH-substituted arenes from 1-(Diazo-2,2,2-trifluoroethyl)arenes
-
Arenes substituted with perfluoroalkyl groups are attractive targets for drug and agrochemical development. Exploiting the carbenic character of donor/acceptor diazo compounds, a diversity-oriented synthesis of perfluoroalkylated arenes, for late stage fluorofunctionalization, is described. The reaction of 1-(diazo-2,2,2-trifluoroethyl)arenes with HF, F/Br, F2, CF3H, and CF3SH sources give direct access to a variety of perfluoroalkyl-substituted arenes presenting with incremental fluorine content. The value of this approach is also demonstrated for radiochemistry and positron emission tomography with the [18F]-labeling of CF3CHF-, CF3CBrF-, and CF3CF2-arenes from [18F]fluoride.
- Emer, Enrico,Twilton, Jack,Tredwell, Matthew,Calderwood, Samuel,Collier, Thomas Lee,Ligault, Benot,Taillefer, Marc,Gouverneur, Vronique
-
supporting information
p. 6004 - 6007
(2015/01/09)
-
- Photoactivation of (p-methoxyphenyl)(trifluoromethyl)diazirine in the presence of phenolic reaction partners
-
Shine light on your chemistry! Irradiating 3-(4-methoxyphenyl)-3- (trifluoromethyl)-3H-diazirine in the presence of equimolar solutions of phenol and tyrosine derivatives leads to Friedel-Crafts alkylations (see scheme), which suggests a strategy for the development of "cleaner" diazirines for chemical biology. Copyright
- Raimer, Bj?rn,Lindel, Thomas
-
supporting information
p. 6551 - 6555
(2013/06/27)
-
- Catalytic asymmetric hydrogenation of α-CF3- or β-CF3-Substituted acrylic acids using Rhodium(I) complexes with a combination of chiral and achiral ligands
-
Only the mixture works! Acrylic acid derivatives with CF3 substituents in α or β position were efficiently hydrogenated in the presence of a RhI complex with a chiral secondary phosphine oxide (SPO; see scheme) and an achiral Ph3P as ligands. The corresponding propanoic acid derivatives were obtained with generally high conversion (>99 %) and high enantioselectivity (92->99 %). Copyright
- Dong, Kaiwu,Li, Yang,Wang, Zheng,Ding, Kuiling
-
supporting information
p. 14191 - 14195
(2014/01/06)
-
- Highly efficient synthesis of aryl and heteroaryl trifluoromethyl ketones via o-iodobenzoic acid (IBX)
-
A two-step process for the synthesis of aryl and heteroaryl trifluoromethyl ketones from the corresponding aldehydes is described. Trifluoromethyl alcohols were prepared from aryl and heteroaryl aldehydes in excellent yields using catalytic amount of K2CO3. The trifluoromethyl alcohols were then oxidized conveniently and efficiently by o-iodoxybenzoic acid (IBX) under mild conditions to get the desired functionalized aryl and heteroaryl trifluoromethyl ketones.
- Cheng, Huicheng,Pei, Yu,Leng, Faqiang,Li, Jingya,Liang, Apeng,Zou, Dapeng,Wu, Yangjie,Wu, Yusheng
-
p. 4483 - 4486
(2013/07/26)
-
- A coupling of benzamides and donor/acceptor diazo compounds to form γ-lactams via Rh(III)-catalyzed C-H activation
-
The coupling of O-pivaloyl benzhydroxamic acids with donor/acceptor diazo compounds provides isoindolones in high yield. The reaction tolerates a broad range of benzhydroxamic acids and diazo compounds, including substituted 2,2,2-trifluorodiazoethanes. Mechanistic experiments suggested that C-H activation is turnover-limiting and irreversible and that insertion of the diazo compound favors electron-deficient substrates.
- Hyster, Todd K.,Ruhl, Kyle E.,Rovis, Tomislav
-
supporting information
p. 5364 - 5367
(2013/05/22)
-
- Oxidation of α-trifluoromethyl alcohols using a recyclable oxoammonium salt
-
A simple, mild method for the oxidation of α-trifluoromethyl alcohols to trifluoromethyl ketones (TFMKs) using the oxoammonium salt 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate (1) is described. Under basic conditions, oxidation proceeds rapidly and affords good to excellent yields of TFMKs, without concomitant formation of the hydrate. The byproduct of the oxidation, 4-acetylamino-2,2,6,6-tetramethyl-1- piperidinyloxy (1c), is easily recovered and can be conveniently reoxidized to regenerate the oxoammonium salt.
- Kelly, Christopher B.,Mercadante, Michael A.,Hamlin, Trevor A.,Fletcher, Madison H.,Leadbeater, Nicholas E.
-
p. 8131 - 8141
(2013/01/15)
-
- 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)
-
- Aggregation induced emission (AIE) of trifluoromethyl substituted distyrylbenzenes
-
The AIE properties of two trifluoromethyl substituted distyrylbenzene model compounds were compared. The fluorescence quantum efficiency of these molecules can be modulated by tuning their subtle solid-state intermolecular interactions.
- Shi, Zhengwei,Davies, Joshua,Jang, Sei-Hum,Kaminsky, Werner,Jen, Alex K.-Y.
-
supporting information; experimental part
p. 7880 - 7882
(2012/08/28)
-
- A Weinreb amide approach to the synthesis of trifluoromethylketones
-
A novel route to access trifluoromethylketones (TFMKs) from Weinreb amides is reported. This represents the first documented case of the Ruppert-Prakash reagent (TMS-CF3) reacting in a constructive manner with an amide and enables synthesis of TMFKs without risk of over-trifluoromethylation.
- Rudzinski, Diandra M.,Kelly, Christopher B.,Leadbeater, Nicholas E.
-
supporting information
p. 9610 - 9612
(2012/10/29)
-
- A photoreactive probe that differentiates the binding sites of noncompetitive GABA receptor antagonists
-
γ-Aminobutyric acid (GABA) receptors are postsynaptic membrane protein complexes that are important not only in the regulation of the nervous system but also as targets of drugs and insecticides. We synthesized a photoreactive straight-chain noncompetitiv
- Shimotahira, Hiroshi,Fusazaki, Sayaka,Ikeda, Izumi,Ozoe, Yoshihisa
-
supporting information; experimental part
p. 1598 - 1600
(2011/05/11)
-
- 4-AMINO-5-OXO-7, 8-DIHYDROPYRIMIDO [5,4-F] [1,4] OXAZEPIN-6 (5H) -YL) PHENYL DERIVATIVES, PHARMACEUTICAL COMPOSITIONS AND USES THEREOF
-
The invention provides compounds of Formula (I), wherein R1, R2a, R2b, R3, m and A are as defined herein, as well as compositions thereof and methods for treating a disease, condition or disorder that is modulated by the inhibition of the diacylglycerol O-acyltransferase 1 (DGAT-1) enzyme by administering the compounds of the present invention and/or compositions thereof.
- -
-
Page/Page column 48
(2010/08/09)
-
- 4-AMINO-7,8-DIHYDROPYRIDO[4,3-d]PYRIMIDIN-5(6H)-ONE DERIVATIVES
-
The invention provides compounds of the general Formula (I) where R1, R2, and A are defined herein, as well as the preparation, compositions and uses thereof.
- -
-
Page/Page column 37
(2010/08/08)
-
- Hyperbranched polymers with controlled degree of branching from 0 to 100%
-
A linear polymer, hyperbranched polymers with various degrees of branching, and 100% hyperbranched polymers were successfully synthesized by self-polycondensation of 2,2,2-trifluoro-1-[4-(4-phenoxyphenoxy)phenyl]ethanone by using different amounts of trifluoromethanesulfonic acid from the same AB2 monomer.
- Segawa, Yukari,Higashihara, Tomoya,Ueda, Mitsuru
-
supporting information; experimental part
p. 11000 - 11001
(2010/09/17)
-
- Enantioselective synthesis of β-trifluoromethyl α-amino acids
-
Figure presented We report herein the three-step enantioselective synthesis of β-trifluoromethyl α-amino acids including trifluorovaline (TFV) using stereoselective hydrogenation with [((R)-trichickenfootphos)Rh(cod)] BF4 catalyst as the key st
- Benhaim, Cyril,Bouchard, Luc,Pelletier, Guillaume,Sellstedt, John,Kristofova, Livia,Daigneault, Sylvain
-
supporting information; experimental part
p. 2008 - 2011
(2010/07/06)
-
- A high performance oxidation method for secondary alcohols by inductive activation of TEMPO in combination with pyridine-bromine complexes
-
A new TEMPO-mediated catalytic oxidation method in combination with Py·HBr3 (stoichiometric) is developed for oxidation of secondary alcohols to the corresponding ketones. The performance of this oxidizing system is better compared with that of TEMPO method combined with R4NBr3. Poly(4-vinylpyridine)·HBr3 can be used in place of Py·HBr3. The electron-withdrawing substituent at the C-4 position of TEMPO increases the reactivity of TEMPO significantly in the oxidation of electron-deficient alcohols such as polyhaloalkylmethanols. Inductive effect of the substituent of TEMPO is discussed through the characterization of the redox potential of N-O radical by cyclic voltammetry.
- Mei, Zhen-Wu,Omote, Takumi,Mansour, Mounir,Kawafuchi, Hiroyuki,Takaguchi, Yutaka,Jutand, Anny,Tsuboi, Sadao,Inokuchi, Tsutomu
-
scheme or table
p. 10761 - 10766
(2009/04/11)
-
- Silver compounds in synthetic chemistry. Part 5: Selective syntheses of trifluoromethylketones, RCOCF3, from trifluoromethylsilver, AgCF3, and corresponding acyl chlorides, RCOCl
-
Trifluoromethylketones of aromatics, heteroaromatics and olefins are formed selectively from reactions of trifluoromethylsilver and the corresponding carboxylic acid chlorides in moderate to excellent yields. The conditions chosen are dependent on the nature of the acyl chloride. Attempts to prepare alkyl(trifluoromethyl)ketones yielded product mixtures of the corresponding acyl fluorides, trifluoromethyl-, pentafluoroethyl- and n-heptafluoropropyl ketones.
- Kremlev, Mikhail M.,Mushta, Aleksej I.,Tyrra, Wieland,Naumann, Dieter,Fischer, Hendrik T.M.,Yagupolskii, Yurii L.
-
p. 1385 - 1389
(2008/09/18)
-
- Lewis base-catalyzed perfluoroalkylation of carbonyl compounds and imines with (perfluoroalkyl)trimethylsilane
-
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
-
p. 1133 - 1145
(2007/10/03)
-
- Palladium-catalyzed regio- and stereoselective formate reduction of fluorine-containing allylic mesylates. A new entry for the construction of a tertiary carbon attached with a fluoroalkyl group
-
The regioselective palladium-catalyzed formate reduction of γ-fluoroalkylated allylic esters is described. Reduction of the allylic esters under the influence of palladium with a monodentate phosphine ligand proceeded preferentially at the γ position, the corresponding reduction products with a fluoroalkyl group at the tertiary carbon being afforded in high yields. When the chiral allylic ester was employed, complete chirality transfer was observed, leading to the optically active materials in high yields.
- Konno, Tsutomu,Takehana, Tsuyoshi,Mishima, Makoto,Ishihara, Takashi
-
p. 3545 - 3550
(2007/10/03)
-
- Design, synthesis and evaluation of novel hydroxyamides as orally available anticonvulsants
-
Themisone, also known as Atrolactamide, was found, in the 1950s, to be a very potent anticonvulsant. It was hypothesized that the -CF3 substitution would maintain the anticonvulsant activity. Anticonvulsant testing of our novel compounds by the
- Schenck, Hilary A.,Lenkowski, Paul W.,Choudhury-Mukherjee, Indrani,Ko, Seong-Hoon,Stables, James P.,Patel, Manoj K.,Brown, Milton L.
-
p. 979 - 993
(2007/10/03)
-
- FLUORINATED PHENYL-NAPHTHALENYL-UREA COMPOUNDS AS INHIBITORS OF CYTOKINES INVOLVED IN INFLAMMATORY PROCESSES
-
Disclosed are compounds of formula (I) wherein R1, R2, W and X of formula (I) are defined herein. The compounds inhibit production of cytokines involved in inflammatory processes and are thus useful for treating diseases and pathological conditions involving inflammation such as chronic inflammatory disease. Also disclosed are processes for preparing these compounds and pharmaceutical compositions comprising these compounds.
- -
-
-
- Total synthesis of two photoactivatable analogues of the growth-factor-like mediator sphingosine 1-phosphate: Differential interaction with protein targets
-
The first synthesis of two photoreactive analogues of the lipid mediator and second messenger sphingosine 1-phosphate (S1P), [32P]-labeled (2S,3R)-14-O-(4′-benzoylphenyl)- and (2S,3R)-14-O-((4′ -trifluoromethyldiazirinyl)phenyl)-(4E) -tetradece
- Lu, Xuequan,Cseh, Sandor,Byun, Hoe-Sup,Tigyi, Gabor,Bittman, Robert
-
p. 7046 - 7050
(2007/10/03)
-
- Process for preparing alpha-halogenated retones
-
The invention concerns a method for preparing α-halogenated ketones from secondary α-halogenated alcohols. More particularly, the invention concerns the preparation of α-trihalogenated ketones from secondary α-trihalogenated alcohols. The method for prepa
- -
-
-
- Oxime derivatives and the use thereof as latent acids
-
Compounds of formula I, II and III, wherein wherein R1is for example hydrogen, C1-C12alkyl, C3-C30cycloalkyl, C2-C12alkenyl, C4-C8cycloalkenyl, phenyl, whic
- -
-
-