The reaction between (bromodifluoromethyl)trimethylsilane (TMSCFBr) and potassium thiocyanate providing TMSCFNCS is described. The process involves the interaction of difluorocarbene with the nitrogen atom of the thiocyanate anion. The obtained silicon reagent served as a source of the fluorinated group and difluorocarbene in the reaction with -alkyl imines, affording 2-(difluoromethylthio)-4-fluoroimidazoles.
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http://dx.doi.org/10.1021/acs.orglett.4c04038 | DOI Listing |
Org Lett
December 2024
N. D. Zelinsky Institute of Organic Chemistry, 119991 Moscow, Leninsky prosp. 47, Russian Federation.
Chemistry
December 2023
N. D. Zelinsky Institute of Organic Chemistry, 119991, Moscow, Leninsky prosp. 47, Russian Federation.
A metal-free one-pot process for the gem-difluoroolefination of amides is described. The reaction is based on interaction of generated in situ α-chloroiminium salts with difluorinated phosphorus ylide formed from difluorocarbene and triphenylphosphine. The olefination involves nucleophile-assisted dephosphorylation and proceeds within one hour at low temperature.
View Article and Find Full Text PDFInorg Chem
January 2023
Department of Applied Chemistry, National Chiayi University, Chiayi60004, Taiwan.
J Org Chem
January 2023
Enamine Ltd., Chervonotkatska Str. 78, Kyïv 02094, Ukraine.
The reaction of trimethyl(trifluoromethyl)silane-tetrabutylammonium difluorotriphenylsilicate (CFSiMe-TBAT) with a series of imidazoles gives products of the formal difluorocarbene insertion into the C-H bond at the C-2 position (i.e., -difluoromethylation).
View Article and Find Full Text PDFJ Comput Chem
October 2022
Department of Applied Chemistry, National Chiayi University, Chiayi, Taiwan.
The trapping reactions of carbene analogs G14F (G14 = group 14 element) by the benzene-bridged B/P-Rea frustrated Lewis pair (FLPs) molecule are studied using density functional theory (B3LYP-D3(BJ)/def2-TZVP). Our theoretical investigations predict that only the CF intermediate rather than other heavy carbene analogs can be trapped by the B/P-Rea FLP-type molecule. Energy decomposition analysis-natural orbitals for chemical valence (EDA-NOCV) analyses indicate that the bonding nature of the G14F catching reactions by the B/P-Rea FLP-type molecule is a donor-acceptor (singlet-singlet) interaction rather than an electron-sharing (triplet-triplet) interaction.
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