82907-00-4Relevant articles and documents
The organic group is substituted with a fluorine-containing olefin production
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Paragraph 0094, (2019/01/06)
PROBLEM TO BE SOLVED: To provide a production method that can produce a fluorine-containing olefin substituted with an organic group from a fluorine-containing olefin conveniently and efficiently (high yield, high selectivity, low cost).SOLUTION: The method for producing a fluorine-containing olefin substituted with an organic group includes a step of reacting a fluorine-containing olefin with an organosilicon compound in the presence of an organic transition metal catalyst containing a transition metal selected from among nickel, palladium, platinum, rhodium, ruthenium and cobalt.
Copper-mediated one-pot synthesis of trifluorostyrene derivatives from tetrafluoroethylene and arylboronate
Kikushima, Kotaro,Sakaguchi, Hironobu,Saijo, Hiroki,Ohashi, Masato,Ogoshi, Sensuke
supporting information, p. 1019 - 1021 (2015/08/24)
We developed the copper-mediated synthesis of trifluorostyrene derivatives. β-Fluorine elimination of a 2-aryl-1,1,2,2- tetrafluoroethylcopper complex, generated in situ from arylboronate, copper tert-butoxide, and 1,10-phenanthroline with tetrafluoroethylene (TFE) via carbocupration, was promoted by the addition of a Lewis acid. The present reaction system was applied to the one-pot synthesis of various trifluorostyrene derivatives, through the transmetalationcarbocuprationβ-fluorine elimination sequence.
Base-free Hiyama coupling reaction via a group 10 metal fluoride intermediate generated by C-F bond activation
Saijo, Hiroki,Sakaguchi, Hironobu,Ohashi, Masato,Ogoshi, Sensuke
supporting information, p. 3669 - 3672 (2014/08/18)
A Pd(0)-catalyzed Hiyama coupling reaction of tetrafluoroethylene (TFE) proceeded without the use of a base to give α,β,β- trifluorostyrene derivatives. A Ni(0)-catalyzed Hiyama coupling reaction of perfluoroarenes also occurred without a base. The key intermediate in these reactions would be a transition-metal fluoride complex that is generated in situ by the oxidative addition of a C-F bond.
Palladium-catalyzed base-free Suzuki-Miyaura coupling reactions of fluorinated alkenes and arenes via a palladium fluoride key intermediate
Ohashi, Masato,Saijo, Hiroki,Shibata, Mitsutoshi,Ogoshi, Sensuke
supporting information, p. 443 - 447 (2013/02/26)
A new strategy for C-C bond formation with organoboronates through C-F activation of fluorinated alkenes and arenes was developed. In this Pd-catalyzed Suzuki-Miyaura-type cross-coupling reaction, neither a base for enhancing the reactivity of the organoboron reagents nor a Lewis acid for promoting C-F bond activation was required. A fluoropalladium intermediate played an essential role in this reaction. In addition, a Ni(NHC) catalyst was efficient for C-C coupling through C-F bond activation of fluoroarenes. Pd0/PR 3 complexes promote C-C bond formation with organoboronates through C-F bond activation of fluorinated alkenes. Mechanistic studies show that a PdII fluoride intermediate plays an essential role in this base-free cross-coupling reaction. Moreover, a Ni(NHC) catalyst is efficient for C-C coupling through C-F bond cleavage of fluoroarenes. Copyright
Preparation of trifluorostyrenes via palladium-catalyzed coupling of arylboronic acids with chloro- and bromotrifluoroethylene
Xu, Chunfa,Chen, Sheng,Lu, Long,Shen, Qilong
, p. 10314 - 10320 (2013/01/15)
A highly efficient and cost-effective method for the preparation of α,β,β-trifluorostyrene (TFS) and its derivatives is described. The method required only 0.2 mol % of Pd(dba)2 and 0.4 mol % of PtBu3 and occurred to full conversion within 2.0 h. With this method, a wide range of arylboronic acids were efficiently incorporated to generate α,β,β-trifluorostyrene derivatives.
Pd-catalyzed arylation of chlorotrifluoroethylene using arylboronic acids
Yamamoto, Tetsuya,Yamakawa, Tetsu
supporting information; experimental part, p. 3454 - 3457 (2012/08/29)
The palladium-catalyzed cross-coupling of chlorotrifluoroethylene and arylboronic acids proceeds in the presence of a base and H2O to provide α,β,β-trifluorostyrene derivatives in satisfactory yields.
Synthesis of trifluorostyrene derivatives by palladium-catalyzed cross-coupling of lithium trimethoxy(trifluorovinyl)borate with aryl bromides
Duric, Sasa,Schmidt, Bernd M.,Ninnemann, Nina M.,Lentz, Dieter,Tzschucke, C. Christoph
supporting information; experimental part, p. 437 - 441 (2012/02/15)
Fluor-ing it: The stable, crystalline trimethoxy(trifluorovinyl)borate is a convenient reagent for efficiently displacing a bromine atom with a trifluorovinyl group (see scheme). This Suzuki coupling reaction significantly simplifies the route to trifluor
METHOD FOR PRODUCING SUBSTITUTED FLUORINE-CONTAINING OLEFIN
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Page/Page column 9, (2013/02/28)
This invention relates to a method of reacting fluoroolefin with an organic magnesium compound in the presence of a catalyst comprising nickel or palladium so as to efficiently produce fluoroolefin, such as TFE, in which a fluorine (F) atom or atoms bonded to the sp2 hybridized carbon atom are substituted with an organic group.
Palladium-catalyzed coupling reactions of tetrafluoroethylene with arylzinc compounds
Ohashi, Masato,Kambara, Tadashi,Hatanaka, Tsubasa,Saijo, Hiroki,Doi, Ryohei,Ogoshi, Sensuke
supporting information; experimental part, p. 3256 - 3259 (2011/04/24)
Organofluorine compounds are widely used in all aspects of the chemical industry. Although tetrafluoroethylene (TFE) is an example of an economical bulk organofluorine feedstock, the use of TFE is mostly limited to the production of poly(tetrafluoroethylene) and copolymers with other alkenes. Furthermore, no catalytic transformation of TFE that involves carbon-fluorine bond activation has been reported to date. We herein report the first example of a palladium-catalyzed coupling reaction of TFE with arylzinc reagents in the presence of lithium iodide, giving α,β,β-trifluorostyrene derivatives in excellent yields.
An efficient dehyrohalogenation method for the synthesis of α,β,β-trifluorostyrenes, α-chloro-β,β- difluorostyrenes and E-1-arylperfluoroalkenes
Anilkumar,Burton, Donald J.
, p. 1174 - 1184 (2007/10/03)
Dehydrofluorination of 1-aryl-1,2,2,2-tetrafluoroethanes (ArCHFCF 3) and 1-aryl-1-chloro-2,2,2-trifluoroethane (ArCHClCF3) using lithiumhexamethyldisilazide (LHMDS) in tetrahydrofuran (THF) at room temperature produced 1,2,2-trifluorostyrene and 1-chloro-2,2-difluorostyrene, respectively, in very good isolated yields. Dehydrofluorination of 1,2,2,3,3,3-hexafluoro-1-phenyl-propane (PhCHFCF2CF3) and 1,2,2,3,3,4,4,4-octafluoro-1-phenyl-butane (PhCHFCF2CF 2CF3) using LHMDS produced the corresponding substituted olefins (1-phenyl-1,2,3,3,3-pentafluoroprop-1-ene and 1-phenyl-1,2,3,3,4,4,4- pentafluorobut-1-ene) in good yield and high E-selectivity. Dehydrofluorination of 1-chloro-1-phenyl-2,2,3,3,3-pentafluoropropane (PhCHClCF2CF 3) and 1-chloro-1-phenyl-2,2,3,3,4,4,4-heptafluorobutane (PhCHClCF2CF2CF3) produced a mixture of the corresponding E and Z olefins (PhCClCFCF3 and PhCClCFCF 2CF3) in good yield.
