- Selective electrochemical synthesis and reactivity of functional benzylic fluorosilylsynthons
-
Electrochemical reductive silylation of meta-(trifluoromethyl)arenes by the sacrificial anode technique selectively led to meta-trimethylsilyldifluoromethylarenes (ArCF2TMS), in the presence of an excess of TMSCl and in a THF/cosolvent mixture
- Clavel, Philippe,Lessene, Guillaume,Biran, Claude,Bordeau, Michel,Roques, Nicolas,Trévin, Stéphane,Montauzon, Dominique De
-
-
Read Online
- Mg-Cu bimetal system for selective C-F bond activation
-
Bimetal system of Mg-CuCl in DMI for selective C-F and C-Cl bonds activation has been examined. This article involves (1) a short overview of bimetal system of Mg-metals for selective C-F bond activation, (2) C-F bond activation of alkyl trifluoroacetates
- Utsumi, Shinya,Katagiri, Toshimasa,Uneyama, Kenji
-
-
- Cu-deposits on Mg metal surfaces promote electron transfer reactions
-
The enhancement of the electron transfer processes in the Grignard reagent formation-type ring silylation and the defluorination-silylation of perfluoroalkyl benzenes by Cu(0)-deposited Mg metal were confirmed. Microscopic analysis and substituent effects implied a different reduction process in the presence of Cu-deposited Mg metal than in the presence of bare Mg metal.
- Utsumi, Shinya,Katagiri, Toshimasa,Uneyama, Kenji
-
experimental part
p. 1085 - 1091
(2012/03/07)
-
- Preparation of (phenyldifluoromethyl)- and (phenoxydifluoromethyl)-silanes by magnesium-promoted carbon-chlorine bond activation
-
Treatment of α-chloro-α,α-difluorotoluene and α-chloro-α,α-difluoroanisole with chlorotrimethylsilane in the presence of magnesium in DMF led to their corresponding trimethylsilyl derivatives. These compounds are able to transfer their fluorinated group to various electrophilic substrates (carbonyl compounds, disulfides, phenyl isocyanate).
- Guidotti, Jér?me,Metz, Fran?ois,Tordeux, Marc,Wakselman, Claude
-
p. 1759 - 1762
(2007/10/03)
-
- Selective electrosynthesis of (trimethylsilyldifluoro)methylbenzene, a PhCF2-precursor; conditions for a molar scale preparation without HMPA
-
Electrochemical reductive silylation of trifluoromethylbenzene by the sacrificial anode technique selectively led, in a THF/DMPU mixture instead of THF/HMPA and according to the charge passed, to the corresponding mono-, bis- or tris-trimethylsilyl derivatives, respectively PhCF2TMS, PhCF(TMS)2 and PhC(TMS)3. This reaction, without any chemical equivalent, was extended to a molar scale synthesis, using a tubular flow cell.
- Clavel,Léger-Lambert,Biran,Serein-Spirau,Bordeau,Roques,Marzouk
-
p. 829 - 834
(2007/10/03)
-
- Nucleophilic introduction of fluorinated alkyl groups into aldehydes and ketones using the corresponding alkyl halide with samarium(II) iodide
-
Fluorinated alkyl groups such as PhCF2, C6F13, CF3CCl2 and CF2CO2Et are nucleophilically introduced into an aldehyde or ketone using fluorinated alkyl halides with SmI2/sub
- Yoshida, Masato,Suzuki, Daiki,Iyoda, Masahiko
-
p. 643 - 648
(2007/10/03)
-
- -
-
The sacrificial anode electrochemical technique, using an undivided cell and a constant current density, provides a nice preparative route for creating Si-Si and C-Si bonds without using alkali metals. Compared to the chemical organometallic synthesis, this method is extremely selective and can lead to original compounds not accessible by the chemical routes. Bases, such as the 2-pyrrolidone magnesium salt electrogenerated in the same conditions, allowed the stereoselective synthesis of Z-silyl enol ethers. Finally, the reduction potentials of a large number of chlorosilanes measured by cyclic voltammetry in standard conditions are reported.
- Biran,Bordeau,Bonafoux,Deffieux,Duprat,Jouikov,Leger-Lambert,Moreau,Serein-Spirau
-
p. 591 - 600
(2007/10/03)
-