AI Article Synopsis

  • The reaction describes how (bromodifluoromethyl)trimethylsilane (TMSCFBr) interacts with potassium thiocyanate to produce TMSCFNCS.
  • The process involves difluorocarbene reacting with the nitrogen atom in the thiocyanate ion.
  • The resulting silicon compound is used to introduce fluorinated groups into -alkyl imines, leading to the formation of 2-(difluoromethylthio)-4-fluoroimidazoles.

Article Abstract

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.4c04038DOI Listing

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Article Synopsis
  • The reaction describes how (bromodifluoromethyl)trimethylsilane (TMSCFBr) interacts with potassium thiocyanate to produce TMSCFNCS.
  • The process involves difluorocarbene reacting with the nitrogen atom in the thiocyanate ion.
  • The resulting silicon compound is used to introduce fluorinated groups into -alkyl imines, leading to the formation of 2-(difluoromethylthio)-4-fluoroimidazoles.
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gem-Difluoroolefination of Amides.

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December 2023

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Article Synopsis
  • The study uses density functional theory to explore how benzene-bridged frustrated Lewis pairs (FLPs) can trap certain species, finding that all Group-13/P-based FLPs can do so energetically, while only the B/P group from the B/Group-15 FLPs is effective.
  • The atomic radius of the Group-15 Lewis base affects reactivity in these trapping reactions, whereas the atomic radius of the Group-13 Lewis acid does not influence activation barriers.
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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).

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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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