- Trifluoromethyl Thianthrenium Triflate: A Readily Available Trifluoromethylating Reagent with Formal CF3+, CF3?, and CF3-Reactivity
-
Here we report the synthesis and application of trifluoromethyl thianthrenium triflate (TT-CF3+OTf-) as a novel trifluoromethylating reagent, which is conveniently accessible in a single step from thianthrene and triflic anhydride. We demonstrate the use of TT-CF3+OTf- in electrophilic, radical, and nucleophilic trifluoromethylation reactions.
- Jia, Hao,H?ring, Andreas P.,Berger, Florian,Zhang, Li,Ritter, Tobias
-
supporting information
p. 7623 - 7628
(2021/05/26)
-
- COMPLEXES FOR NUCLEOPHILIC, RADICAL, AND ELECTROPHILIC POLYFLUOROALKYLATION
-
Disclosed herein are borazine complexes and use of the same in perfluoroalkylation reactions.
- -
-
Paragraph 00136; 00138
(2018/04/11)
-
- Design, synthesis and evaluation of novel 19F magnetic resonance sensitive protein tyrosine phosphatase inhibitors
-
Fluorine is a highly attractive element for both medicinal chemistry and imaging technologies. To facilitate protein tyrosine phosphatase (PTP)-targeted drug discovery and imaging-guided PTP research on fluorine, several highly potent and 19F MR sensitive PTP inhibitors were discovered through a structure-based focused library strategy.
- Li, Yu,Xia, Guiquan,Guo, Qi,Wu, Li,Chen, Shizhen,Yang, Zhigang,Wang, Wei,Zhang, Zhong-Yin,Zhou, Xin,Jiang, Zhong-Xing
-
p. 1672 - 1680
(2016/08/24)
-
- Organocatalysis approach to trifluoromethylation with fluoroform
-
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
-
supporting information
p. 367 - 371
(2014/01/06)
-
- Trifluoromethylation of ketones and aldehydes with Bu3SnCF 3
-
The (trifluoromethyl)stannane reagent, Bu3SnCF3, was found to react under CsF activation with ketones and aldehydes to the corresponding trifluoromethylated stannane ether intermediates at room temperature in high yield. Only a mildly acidic extraction (aqueous NH 4Cl) is required to release the corresponding trifluoromethyl alcohol products. The protocol is compatible with acid-sensitive functional groups.
- Sanhueza, Italo A.,Bonney, Karl J.,Nielsen, Mads C.,Schoenebeck, Franziska
-
p. 7749 - 7753
(2013/09/02)
-
- Structure-Activity Relationships of Organofluorine Inhibitors of β-Amyloid Self-Assembly
-
A broad group of structurally diverse small organofluorine compounds were synthesized and evaluated as inhibitors of β-amyloid (Aβ) self-assembly. The main goal was to generate a diverse library of compounds with the same functional group and to observe general structural features that characterize inhibitors of Aβ oligomer and fibril formation, ultimately identifying structures for further focused inhibitor design. The common structural motifs in these compounds are CF3-C-OH and CF3-C-NH groups that were proposed to be binding units in our previous studies. A broad range of potential small-molecule inhibitors were synthesized by combining various carbocyclic and heteroaromatic rings with an array of substituents, generating a total of 106 molecules. The compounds were tested by standard methods such as thioflavin-T fluorescence spectroscopy for monitoring fibril formation, biotinyl Aβ1-42 single-site streptavidin-based assays for observing oligomer formation, and atomic force microscopy for morphological studies. These assays revealed a number of structures that show significant inhibition against either Aβ fibril or oligomer formation. A detailed analysis of the structure-activity relationship of anti-fibril and -oligomer properties is provided. These data present further experimental evidence for the distinct nature of fibril versus oligomer formation and indicate that the interaction of the Aβ peptide with chiral small molecules is not stereospecific in nature.
- Toeroek, Bela,Sood, Abha,Bag, Seema,Kulkarni, Aditya,Borkin, Dmitry,Lawler, Elizabeth,Dasgupta, Sujaya,Landge, Shainaz,Abid, Mohammed,Zhou, Weihong,Foster, Michelle,Levine, Harry,Toeroek, Marianna
-
experimental part
p. 910 - 919
(2012/08/28)
-
- Efficient synthesis of tetradecafluoro-4-phenylheptan-4-ol by a Cannizzaro-type reaction and application of the alcohol as a bulky Martin ligand variant for a new anti-apicophilic phosphorane
-
Alcohols 8 bearing two identical perfluoroalkyl groups were prepared by the reaction of the corresponding perfluoroalkyl phenyl ketones 7 with 0.5 equivalents of t-BuOK via Cannizzaro-type disproportionation. Utilizing the new bulky bidentate ligand with two n-C3F7 groups generated from 8c, anti-apicophilic phosphorane 5a and its stable isomer 6a were synthesized. The crystal structures of 5a and 6a were slightly affected by the steric repulsion of heptafluoropropyl groups. Kinetic studies on the isomerization of 5a to 6a showed that the new ligand was effective for decreasing the isomerization rate compared with its C2F5 analog 3a to about half.
- Jiang, Xin-Dong,Matsukawa, Shiro,Kakuda, Ken-Ichiro,Fukuzaki, Yuta,Zhao, Wei-Li,Li, Lin-Song,Shen, Huai-Bin,Kojima, Satoshi,Yamamoto, Yohsuke
-
scheme or table
p. 9823 - 9829
(2011/01/07)
-
- Convenient syntheses of 1,1,1,3,3,3-hexafluoro-2-organyl-propan-2-ols and the corresponding trimethylsilyl ethers
-
A new convenient synthetic procedure to obtain various 1,1,1,3,3,3- hexafluoro-2-organyl-propan-2-ols and the corresponding trimethylsilyl ethers has been worked out starting from anhydrides or activated esters of carboxylic acids and trimethyl(trifluoromethyl)silane in the presence of tetramethylammonium fluoride. Conditions for the selective formation of 1,1,1,3,3,3-hexafluoro-2-organyl-propan-2-ols as well as the trimethylsilyl derivatives have been found.
- Babadzhanova,Kirij,Yagupolskii,Tyrra,Naumann
-
p. 1813 - 1819
(2007/10/03)
-
- Trifluoromethylation of carbonyl compounds with sodium trifluoroacetate
-
In the presence of copper(I) iodide as catalyst, a variety of carbonyl compounds, such as aldehydes, ketones and acid anhydrous, could be trifluoromethylated with sodium trifluoroacetate to give the corresponding alcohols in moderate to high yields, and a possible mechanism was proposed to explain the roles of catalyst and solvent in the reaction system.
- Chang, Ying,Cai, Chun
-
p. 937 - 940
(2007/10/03)
-
- Sodium trifluoroacetate: An efficient precursor for the trifluoromethylation of aldehydes
-
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
-
p. 3161 - 3164
(2007/10/03)
-
- Process of use in perfluoroalkyation and reactant for making use of this process
-
The subject-matter of the present invention is a process of use in perfluoroalkylation and a reactant for making use of this process. This process is defined in that it comprises a stage in which a material of formula RfH and a base (or a species capable of generating a base) are brought into contact, in a polar and anhydrous medium, with a substrate carrying at least one electrophilic functional group. Application to organic synthesis.
- -
-
-
- Nucleophilic trifluoromethylation of acyl chlorides using the trifluoromethyl iodide/TDAE reagent
-
Chemoselective bis-trifluoromethylation of acyl chlorides using the CF3I/TDAE-derived nucleophilic trifluoromethyl anion reagent is reported. Very high yields are obtained of an ester product formed by sequential nucleophilic bis-trifluoromethylation, followed by acylation of the resultant alcoholate.
- Takechi, Naoto,A?t-Mohand, Samia,Médebielle, Maurice,Dolbier Jr., William R.
-
p. 4317 - 4319
(2007/10/03)
-
- Perfluoroalkylation method and reagent therefor
-
PCT No. PCT/FR96/01854 Sec. 371 Date Feb. 22, 1999 Sec. 102(e) Date Feb. 22, 1999 PCT Filed Nov. 22, 1996 PCT Pub. No. WO97/19038 PCT Pub. Date May 29, 1997The subject-matter of the present invention is a process of use in perfluoroalkylation and a reactant for making use of this process. This process is defined in that it comprises a stage in which a material of formula RfH and a base (or a species capable of generating a base) are brought into contact, in a polar and anhydrous medium, with a substrate carrying at least one electrophilic functional group. Application to organic synthesis.
- -
-
-
- PERFLUOROALKYLATION OF BENZENE DERIVATIVES. AN IMPROVED SYNTHESIS OF 1,3-BIS(2-HYDROXYHEXAFLUORO-2-PROPYL)-5-(PERFLUORO-n-ALKYL)BENZENES
-
A three-step high yield synthesis of various 1,3-bis(2-hydroxyhexafluoro-2-propyl)-5-perfluoro-n-alkyl) benzenes is described.Significant improvements in the iodination and perfluoro-alkylation of a perfluoroalkylbenzene diol have been achieved.Copper coupling of straight-chain perfluoroalkyl iodides with the iodobenzene derivative in DMSO gave the desired compounds as DMSO complexes in 78-91 percent yield.
- Sepiol, Janiusz,Soulen, Robert L.
-
-
- Chemiluminescence in the Reaction of a Sulfurane with Alkyl Hydroperoxides
-
The reaction of Martin's sulfurane 1 with tert-butyl hydroperoxide, in the presence of 9,10-dibromoanthracene, emits light in two stages.The early stage, beginning on warming to about -40 deg C, coincides with the formation of olefin, and is intensified by degassing and quenched by oxygen or by organic sulfides.The later stage, seen on warming from -20 to -10 deg C, occurs during the formation of acetone from the hydroperoxide; this luminescence is eliminated by degassing and quenched by 2,6-di-tert-butyl-p-cresol and organic sulfides.Similar phenomena are observed with cumyl hydroperoxide.Relevant observations are reported on the NMR shifts produced in alcohol proton signals by diphenyl sulphoxide and dimethyl sulfoxide and on the CIDNP signals occurring during the reaction.Some conclusions are drawn concerning the mechanism of the luminescence.
- Bartlett, Paul D.,Aida, Tetsuo,Chu, Hsien-Kun,Fang, Tai-Shan
-
p. 3515 - 3524
(2007/10/02)
-