- Synthesis of Trifluoromethylated Dithiocarbamates via Photocatalyzed Substitution Reaction: Pentafluoropyridine as Activating Reagent
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A method for the synthesis of trifluoromethyl-substituted dithiocarbamates from aldehydes is described. The reaction involves nucleophilic trifluoromethylation, derivatization of the silyloxy-group with pentafluoropyridine, and substitution of the fluorin
- Zemtsov, Artem A.,Lunkov, Sergey S.,Levin, Vitalij V.,Dilman, Alexander D.
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- A new and efficient method for the trifluoromethylation of carbonyl compounds with trifluoromethyltrimethylsilane in DMSO
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In the presence of MS 4 ? in DMSO, trifluoromethylation of various aldehydes and ketones with trifluoromethyltrimethylsilane (TMSCF3) proceeded very smoothly to give the corresponding trifluoromethylated adduct in good to quantitative yields wi
- Iwanami, Katsuyuki,Oriyama, Takeshi
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- Tri-tert-butylphosphine is an efficient promoter for the trifluoromethylation reactions of aldehydes, ketones, imides and imines
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A truly catalytic nucleophilic trifluoromethylation reaction of carbonyl compounds with Ruppert's reagent, Me3SiCF3, has been shown to be efficiently promoted by a P(t-Bu)3-DMF system. Imines were also converted to the des
- Mizuta, Satoshi,Shibata, Norio,Sato, Takayuki,Fujimoto, Hiroyuki,Nakamura, Shuichi,Toru, Takeshi
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- Lithium acetate-catalyzed trifluoromethylation of carbonyl compounds with (Trifluoromethyl)trimethylsilane
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Trifluoromethylation of various aldehydes and ketones with (trifluoromethyl)trimethylsilane in the presence of a catalytic amount of a Lewis base such as lithium acetate proceeded smoothly to afford the corresponding trifluoromethylated adducts in good to
- Mukaiyama, Teruaki,Kawano, Yoshikazu,Fujisawa, Hidehiko
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- Organoelement compounds in the electrochemical synthesis of fluoroorganics
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Electrochemical generation of organic anion-radicals in the presence of fluoroorganosilanes causes the chain addition reaction. Adducts of CFCl2SiMe3, CFCl=CFSiMe3 and CF3SiMe3 with benzaldehyde were
- Stepanov
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- Utilisation of ammonium and phosphonium perfluorocyclobutane ylides as fluoride anion source
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Ammonium- and phosphoniumperfluorocyclobutane glides 1 and 2, prepared from perfluorocyclobutene and tertiary amines or phosphines can be used as a masked fluoride anion source. These properties have been demonstrated in several reactions. Ylides 1 and 2 cleave C-Si or O-Si bonds, cause dimerisation of fluoroolefins or react with acid chlorides or activated aromatic compounds under halogen exchange.
- Pasenok, Sergej V.,De Roos, Marijn E.,Appel, Wolfgang K.
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- Tbd-catalyzed trifluoromethylation of carbonyl compounds with (trifluoromethyl)-trimethylsilane
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Trifluoromethylation of carbonyl compounds using (trifluoromethyl) trimethylsilane catalyzed by 1,5,7-triazabicyclo[4,4,0]dec-5-ene (TBD) afforded the corresponding a-trifluoromethyl alcohols in good to excellent yields under mild reaction conditions. Sup
- Matsukawa,Takahashi,Takahashi
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- The direct trifluoromethylsilylation and cyanosilylation of aldehydes: via an electrochemically induced intramolecular pathway
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The initiator-free electrochemical trifluoromethylsilylation and cyanosilylation of aldehydes were developed in an undivided cell. A DFT study reveals that the direct cathodic activation of trimethylsilyl reagents significantly released the congestion around the 'Si' atom, allowing the Si-O bond affinity to form concerted anion intermediates with aldehydes. Thus, intramolecular -CF3 and -CN migration make the reactions much easier to carry out without initiators.
- Yang, Hui,Shen, Yongli,Xiao, Zihui,Liu, Caiyan,Yuan, Kedong,Ding, Yi
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supporting information
p. 2435 - 2438
(2020/03/06)
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- MgCl2-catalyzed trifluoromethylation of carbonyl compounds using (trifluoromethyl)trimethylsilane as the trifluoromethylating agent
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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
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supporting information
p. 6754 - 6762
(2017/11/09)
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- Brook/Elimination/Aldol Reaction Sequence for the Direct One-Pot Preparation of Difluorinated Aldols from (Trifluoromethyl)trimethylsilane and Acylsilanes
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A methodology allowing the one-pot preparation of difluorinated aldols directly from Ruppert-Prakash reagent, acyltrimethylsilanes and aldehydes is reported. The process, initiated by a catalytic amount of an ammonium salt, involves the addition of (trifluoromethyl)trimethylsilane to the acylsilane, followed by a Brook rearrangement and elimination of a fluoride anion that promotes the subsequent aldol reaction. An efficient racemic reaction catalyzed by tetrabutylammonium difluorotriphenylsilicate is described, as well as our first efforts towards an asymmetric version.
- Decostanzi, Mélanie,Godemert, Jérémy,Oudeyer, Sylvain,Levacher, Vincent,Campagne, Jean-Marc,Leclerc, Eric
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p. 526 - 531
(2016/02/27)
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- PERFLUORORALKYLATION OF CARBONYL COMPOUNDS
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The present invention provides a process for producing a compound comprising a perfluorinated alkyl group moiety from a carbonyl compound. Typically, the process includes contacting a carbonyl compound with a silane compound in the presence of a fluorohydrogenate ionic liquid under conditions sufficient to produce a compound comprising a perfluorinated alkyl group. The silane compound includes a perfluoroalkyl group.
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Paragraph 0054; 0055
(2015/07/07)
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- Fe-catalyzed nucleophilic activation of c-si versus allylic C-O bonds: Catalytic trifluoromethylation of carbonyl groups versus tandem trifluormethylation-allylation of olefins
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The nucleophilic ferrate salt Bu4N[Fe(CO)3(NO)] (TBA[Fe]) is able to catalyze the direct trifluoromethylation of aldehydes and ketones using Me3SiCF3 as a trifluoromethylating agent. Interception of the C-Si I-b
- Klein, Johannes E. M. N.,Rommel, Susanne,Plietker, Bernd
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supporting information
p. 5802 - 5810
(2015/01/16)
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- The enantioselective trifluoromethylation of aromatic aldehydes by quaternary ammonium bromide and (IPr)CuF at low catalyst loading
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A general catalytic enantioselective trifluoromethylation of aromatic aldehydes using (IPr)CuF and quinidine-derived quaternary ammonium salt as catalysts has been developed. A wide range of aromatic aldehydes are converted to the corresponding products in up to 92% yield and 81% ee at 2 mol% of catalyst loading.
- Wu, Shaoxiang,Guo, Jiyi,Sohail, Muhammad,Cao, Chengyao,Chen, Fu-Xue
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- Asymmetric trifluoromethylation of aromatic aldehydes by cooperative catalysis with (IPr)CuF and quinidine-derived quaternary ammonium salt
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A general enantioselective trifluoromethylation of aldehydes has been developed using (IPr)CuF and quinidine-derived quaternary ammonium salt as the cooperative catalyst. Thus, a wide range of aromatic aldehydes have been converted to the corresponding products in up to 92% yield and 81% ee at 2 mol% of catalyst loading. The greatly enhanced activity and enantioselectivity result from the initiative generation of active [(IPr)CuCF3] as well as additional coordination activation of other copper species.
- Wu, Shaoxiang,Zeng, Wei,Wang, Qi,Chen, Fu-Xue
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supporting information
p. 9334 - 9337
(2013/01/15)
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- Solkane 365mfc is an environmentally benign alternative solvent for trifluoromethylation reactions
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Solkane 365mfc is introduced for the first time as a new, environmentally benign alternative solvent for nucleophilic trifluoromethylation reactions. The Royal Society of Chemistry 2009.
- Kusuda, Akihiro,Kawai, Hiroyuki,Nakamura, Shuichi,Shibata, Norio
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supporting information; experimental part
p. 1733 - 1735
(2011/03/19)
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- TTMPP-catalyzed trifluoromethylation of carbonyl compounds and imines with trifluoromethylsilane
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A highly basic phosphine, tris(2,4,6-trimethoxyphenyl)phosphine (TTMPP), catalyzes trifluoromethylation using trifluoromethyltrimethylsilane to give the corresponding trifluoromethylated products in good to high yields, with both carbonyl compounds and im
- Matsukawa, Satoru,Saijo, Marina
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p. 4655 - 4657
(2008/09/21)
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- Ammonium bromides/KF catalyzed trifluoromethylation of carbonyl compounds with (trifluoromethyl)trimethylsilane and its application in the enantioselective trifluoromethylation reaction
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The trifluoromethylation of aldehydes and ketones is a potentially powerful method to introduce the CF3 moiety into organic molecules. In general, the trifluoromethylation reaction has been performed by treatment of Me3SiCF3/su
- Mizuta, Satoshi,Shibata, Norio,Hibino, Motoki,Nagano, Shinichi,Nakamura, Shuichi,Toru, Takeshi
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p. 8521 - 8528
(2008/02/09)
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- Lewis acid-catalyzed tri- and difluoromethylation reactions of aldehydes
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The first Lewis acid-catalyzed trifluoromethylation reactions of aldehydes with Me3SiCF3 under TiF4/DMF, Ti(O iPr)4/DMF and Cu(OAc)2/dppp/toluene conditions are described. We have successfu
- Mizuta, Satoshi,Shibata, Norio,Ogawa, Shinichi,Fujimoto, Hiroyuki,Nakamura, Shuichi,Toru, Takeshi
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p. 2575 - 2577
(2008/03/27)
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- Facile synthesis of TMS-protected trifluoromethylated alcohols using trifluoromethyltrimethylsilane (TMSCF3) and various nucleophilic catalysts in DMF
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Organofluorine compounds are becoming increasingly important in different fields, such as material science, agro chemistry, and the pharmaceutical industry. Nucleophilic trifluoromethylation is one of the widely used methods to incorporate a trifluoromethyl moiety into organic molecules. We have carried out extensive studies to develop varieties of easily accessible nucleophilic catalysts to promote such reactions. TMS-protected trifluoromethylated alcohols were prepared from both aldehydes and ketones in excellent yields using catalytic amount of amine N-oxide. Carbonate and phosphate salts also showed efficient catalytic activity toward this reaction. These reactions were highly solvent dependent, and DMF was found to be the most suitable one among the various solvents studied. All these reactions proceeded under very mild conditions, giving clean products and avoiding the use of any fluoride initiators or expensive catalysts, and extremely water-free conditions. The mechanism for the reaction is discussed in detail. DFT calculations were performed on the possible reaction intermediates using the Gaussian 03 program at B3LYP/6-311+G* level to support the proposed mechanism.
- Prakash, G.K. Surya,Panja, Chiradeep,Vaghoo, Habiba,Surampudi, Vijayalakshmi,Kultyshev, Roman,Mandal, Mihirbaran,Rasul, Golam,Mathew, Thomas,Olah, George A.
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p. 6806 - 6813
(2007/10/03)
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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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p. 1133 - 1145
(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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- Trifluoromethylation of carbonyl compounds with trifluoromethyltrimethylsilane (Ruppert reagent) promoted by triphenyldifluorostannates
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Nucleophilic trifluoromethylation of aromatic aldehydes and ketones with trifluoromethyltrimethylsilane is initiated with KF/n-Bu3MeN +HSO4-/Ph3SnF cocatalytic system in CH2Cl2 or with K[Ph3SnF2] in DMF.
- Borkin,Loska,Makosza
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p. 1187 - 1191
(2007/10/03)
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- Towards enantioselective nucleophilic trifluoromethylation
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Various trifluoroacetamides and trifluoromethanesulfinamides, derived from chiral silylated amino alcohols, have been synthesized with the goal of achieving enantioselective nucleophilic trifluoromethylation. The best results were obtained with (R)-phenylglycinol derivatives, but the ee values did not exceed 30%.
- Roussel, Solveig,Billard, Thierry,Langlois, Bernard R.,Saint-James, Laurent
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p. 939 - 944
(2007/10/03)
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- Trifluoromethanesulfinamide from ephedrine: A more efficient trifluoromethylating reagent
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Nucleophilic trifluoromethylation of non-enolizable and enolizable carbonyl compounds was achieved with the trifluoromethanesulfinamide derived from O-silylated ephedrine. In contrast to the trifluoroacetamide analog, previously described, this reagent is able to trifluoromethylate more acidic enolizable compounds.
- Roussel, Solveig,Billard, Thierry,Langlois, Bernard R.,Saint-Jalmes, Laurent
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p. 2119 - 2122
(2007/10/03)
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- Trifluoroacetamides from amino alcohols as nucleophilic trifluoromethylating reagents
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Both non-enolizable and enolizable carbonyl compounds underwent nucleophilic trifluoromethylation by a new family of cheap and efficient trifluoroacetamide reagents derived from vic-amino alcohols (see picture). From an ecological and an economic viewpoint these represent a promising alternative to other known trifluoromethylation reagents.
- Joubert, Jerome,Roussel, Solveig,Christophe, Carole,Billard, Thierry,Langlois, Bernard R.,Vidal, Thierry
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p. 3133 - 3136
(2007/10/03)
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- Trifluoromethylation of nonenolizable carbonyl compounds with a stable piperazino hemiaminal of trifluoroacetaldehyde
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A new stable hemiaminal of fluoral (1) can easily be obtained from the methyl hemiketal of fluoral and N-benzylpiperazine. This white crystalline compound can be used under basic conditions as an efficient nucleophilic trifluoromethylating reagent towards nonenolizable carbonyl compounds.
- Billard, Thierry,Langlois, Bernard R.,Blond, Gaelle
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p. 1467 - 1471
(2007/10/03)
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- New stable reagents for the nucleophilic trifluoromethylation. 1. Trifluoromethylation of carbonyl compounds with N-formylmorpholine derivatives
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equation presented A new stable equivalent of the trifluoromethyl anion has been synthesized from fluoroform. It reacts with nonenolizable carbonyl compounds x such as the Ruppert's reagent.
- Billard,Bruns,Langlois
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p. 2101 - 2103
(2007/10/03)
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- Cesium fluoride catalyzed trifluoromethylation of esters, aldehydes, and ketones with (trifluoromethyl)trimethylsilane
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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.
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p. 2873 - 2876
(2007/10/03)
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- 19F nuclear magnetic resonance spectroscopy for the quantitative detection and classification of carbonyl groups in lignins
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A novel method that permits the quantitative detection and classification of various carbonyl groups in lignins has been developed. The proposed method was optimized with the quantitative trifluoromethylation of a series of carbonyl-containing lignin-like model compounds. This effort was followed by 19F NMR spectral analyses of the resulting fluorine derivatives allowing for a thorough understanding of their structure/19F chemical shift relationships. The various carbonyl groups present in lignins were also investigated by trifluoromethylating them in the presence of catalytic amounts of tetramethylammonium fluoride (TMAF), followed by hydrolysis with TMAF in tetrahydrofuran. By using a variety of selective reactions, it became possible to assign a number of prominent 19F NMR signals to a variety of carbonyl groups present in lignins. These studies demonstrated that the proposed method can be applied to the quantitative determination of carbonyl groups that are present in soluble native and technical lignins.
- Ahvazi, Behzad C.,Crestini, Claudia,Argyropoulos, Dimitris S.
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p. 190 - 201
(2007/10/03)
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- Quantitative trifluoromethylation of carbonyl-containing lignin model compounds
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The efficient trifluoromethylation of a series of carbonyl-containing lignin model compounds was made possible by using Ruppert's reagent in the presence of tetramethylammonium fluoride (TMAF), followed by hydrolysis with aqueous HF. These studies demonstrate that such a method can quantitatively convert carbonyl groups to the CF3-containing compounds, thus qualifying the procedure as a potential analytical tool for the determination of carbonyl groups in lignins.
- Ahvazi,Argyropoulos
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p. 195 - 198
(2007/10/03)
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- 19F Nuclear Magnetic Resonance Spectroscopy for the Elucidation of Carbonyl Groups in Lignins. 1. Model Compounds
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A new method for the detection of different classes of carbonyl groups in a series of carbonyl-containing lignin-like model compounds has been developed. The method is based on the selective fluoride-induced trifluoromethylation of carbonyl groups with (trifluoromethyl)trimethylsilane (TMS-CF3) in the presence of tetramethylammonium fluoride (TMAF), followed by hydrolysis with aqueous HF or TMAF in the case of quinones. In this study a series of ketones, aldehydes, quinones, and dimeric-lignin model compounds were quantitatively trifluoromethylated followed by 19F NMR spectral analyses of the resulting fluorine-containing derivatives, allowing for a thorough understanding of their structure/19F chemical shift relationships. These studies have shown that the 19F-NMR chemical shifts of the trifluoromethyl groups vary significantly and consistently for various classes of carbonyl groups which may be present in complex lignocellulosic materials. These studies are to form the basis for the development of a novel and sensitive method that can be used to obtain quantitative information on the various carbonyl groups present in such materials.
- Ahvazi, Behzad C.,Argyropoulos, Dimitris S.
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p. 2167 - 2175
(2007/10/03)
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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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