3764-36-1Relevant articles and documents
Dehydroxylative Trifluoromethylthiolation, Trifluoromethylation, and Difluoromethylation of Alcohols
Zhang, Wei,Lin, Jin-Hong,Wu, Wenfeng,Cao, Yu-Cai,Xiao, Ji-Chang
supporting information, p. 169 - 172 (2020/01/03)
CF3S, CF3 and HCF2 groups have been identified as valuable functionalities for drug development. Despite significant accomplishments in the trifluoromethylthiolation, trifluoromethylation and difluoromethylation reactions, directly converting common functional groups into CF3S, CF3 or HCF2 groups is still highly desirable. Described here is the dehydroxylative trifluoromethylthiolation, trifluoromethylation and difluoromethylation of alcohols promoted by a R3P/ICH2CH2I system. All of these dehydroxylative reactions were achieved under mild conditions via the activation of the hydroxyl group by the R3P/ICH2CH2I system. A wide substrate scope and good functional group tolerance were observed.
Denitrogenative Hydrotrifluoromethylation of Benzaldehyde Hydrazones: Synthesis of (2,2,2-Trifluoroethyl)arenes
Zhao, Zhensheng,Ma, Kevin C. Y.,Legault, Claude Y.,Murphy, Graham K.
, p. 11240 - 11245 (2019/08/20)
Reacting hydrazones of arylaldehydes with Togni's CF3-benziodoxolone reagent, in the presence of potassium hydroxide and cesium fluoride, induces a denitrogenative hydrotrifluoromethylation event to produce (2,2,2-trifluoroethyl)arenes. This novel reaction was tolerant to many electronically-diverse functional groups and substitution patterns, as well as naphthyl- and heteroaryl-derived substrates. Advantages of this process include the easy access to hydrazone precursors on a large scale, speed and operational simplicity, and being transition metal-free.
Metal-Free Construction of the C(sp3)-CF3 Bond: Trifluoromethylation of Hydrazones with Togni's Reagent under Mild Conditions
Zeng, Huiying,Luo, Zhen,Han, Xinlong,Li, Chao-Jun
, p. 5948 - 5951 (2019/08/29)
A metal-free trifluoromethylation of hydrazones with Togni's reagent under mild conditions was developed. Various functional groups including ester, methoxy, dimethoxy, nitro, halogen, and heterocyclic compounds were tolerated. This simple and green strategy provides a practical tool to construct C(sp3)-CF3 bonds.
Copper-promoted reductive coupling of aryl iodides with 1,1,1-trifluoro-2-iodoethane
Xu, Song,Chen, Huan-Huan,Dai, Jian-Jun,Xu, Hua-Jian
supporting information, p. 2306 - 2309 (2014/05/20)
An efficient Cu-promoted reductive coupling of aryl iodides with 1,1,1-trifluoro-2-iodoethane has been developed. This reaction could occur in good yields under milder conditions as compared with previous studies. The reaction tolerated nitro, formyl, ester, ether, carbonyl, sulfonyl, and even azo groups.
Copper-mediated deoxygenative trifluoromethylation of benzylic xanthates: Generation of a C-CF3 bond from an O-based electrophile
Zhu, Lingui,Liu, Shasha,Douglas, Justin T.,Altman, Ryan A.
, p. 12800 - 12805 (2013/10/01)
The conversion of an alcohol-based functional group, into a trifluoromethyl analogue is a desirable transformation. However, few methods are capable of converting O-based electrophiles into trifluoromethanes. The copper-mediated trifluoromethylation of benzylic xanthates using Umemoto's reagent as the source of CF3 to form C-CF3 bonds is described. The method is compatible with an array of benzylic xanthates bearing useful functional groups. A preliminary mechanistic investigation suggests that the C-CF3 bond forms by reaction of the substrate with in situ generated CuCF3 and CuOTf. Further evidence suggests that the reaction could proceed via a radical cation intermediate. Highly compatible and useful: The copper-mediated trifluoromethylation of benzylic xanthates using Umemoto's reagent as the source of CF3 to form C-CF3 bonds is described (see scheme). The method is compatible with an array of benzylic xanthates bearing useful functional groups. A preliminary mechanistic investigation suggests that the C-CF3 bond forms by reaction of the substrate with in situ generated CuCF3 and CuOTf. Copyright
The use of methyl 2,2-difluoro-2-(fluorosulfonyl)acetate as the difluorocarbene source to generate an in situ source of difluoromethylene triphenylphosphonium ylide
Thomoson, Charles S.,Martinez, Henry,Dolbier Jr., William R.
, p. 53 - 59 (2013/06/26)
Under moderate conditions in the presence of a demethylating reagent, such as iodide, methyl 2,2,-difluoro-2-(fluorosulfonyl)acetate (MDFA) releases difluorocarbene, which in the presence of triphenylphosphine forms difluoromethylene triphenylphosphonium ylide. When the process is carried out also in the presence of aldehydes or activated ketones, the ensuing in situ Wittig-type reaction of the ylide with the carbonyl reactants produces 1,1-difluoroalkenes in good yield. Density Functional Theory calculations were used to provide new estimates of the energies and structures of singlet and triplet states of CH2:, CHF:, and CF2: carbenes, as well as those of their respective triphenylphosphonium ylides.
The palladium-catalyzed cross-coupling reactions of trifluoroethyl iodide with aryl and heteroaryl boronic acid esters
Liang, Apeng,Li, Xinjian,Liu, Dongfeng,Li, Jingya,Zou, Dapeng,Wu, Yangjie,Wu, Yusheng
supporting information; experimental part, p. 8273 - 8275 (2012/09/07)
The cross-coupling reactions of 1,1,1-trifluoro-2-iodoethane with aryl and heteroaryl boronic acid esters have been successfully achieved. The new protocol allows for a convenient introduction of trifluoroethyl groups into a variety of aryl and heteroaryl moieties under mild conditions.
A facile synthesis of isomeric C -(2,2,2-trifluoroethyl)anilines
Trofymchuk, Sergii,Bezdudny, Andrii V.,Pustovit, Yurii M.,Lukin, Oleg,Boyko, Alexander N.,Chekotylo, Alexey,Tolmachev, Andrei A.,Mykhailiuk, Pavel K.
experimental part, p. 1974 - 1976 (2012/08/27)
Three isomers of C-(2,2,2-trifluoroethyl)aniline were prepared on a multigram scale from readily available nitrophenylacetic acids in two steps. First, the carboxy groups of the latter were converted into the trifluoromethyl moieties by treatment with sul
Me3SiCF3/AgF/Cu - A new reagents combination for selective trifluoromethylation of various organic halides by trifluoromethylcopper, CuCF3
Kremlev, Mikhail M.,Mushta, Aleksej I.,Tyrra, Wieland,Yagupolskii, Yurii L.,Naumann, Dieter,M?ller, Angela
experimental part, p. 67 - 71 (2012/03/10)
An alternative copper halide-free route to obtain highly reactive trifluoromethylcopper species has been developed via the reaction of silver fluoride and trimethyl(trifluoromethyl)silane followed by a redox transmetallation with elemental copper. The composition of the reactive intermediate was investigated by means of UV/Vis/NIR, ESR, 19F NMR spectroscopy and ESI mass spectrometry. "Trifluoromethylcopper" prepared by the oxidative transmetallation route exhibits excellent reactivity and selectivity in substitutions of iodine or bromine bond to aromatic or heterocyclic compounds for trifluoromethyl groups without any additional catalyst.
A simple, rapid procedure for nucleophilic radiosynthesis of aliphatic [18F]trifluoromethyl groups
Riss, Patrick J.,Aigbirhio, Franklin I.
, p. 11873 - 11875 (2011/12/04)
A procedure for the radiosynthesis of aliphatic [18F] trifluoromethyl groups by reacting 1,1-difluorovinyl precursors with [ 18F]fluoride ions, resulting in the equivalent of direct nucleophilic addition of H[18F]F, has been developed. A variety of 18F-labelled model compounds were then obtained and two potential [18F]radiotracers were synthesised by a two step process starting from 1,1-difluorovin-2-yl 4-toluenesulfonate. The method is widely applicable for the synthesis of novel radiotracers in high radiochemical yields and good specific activity.
