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Photoreduction of Trifluoromethyl Group: Lithium Ion Assisted Fluoride-Coupled Electron Transfer from EDA Complex.
Uchikura, Tatsuhiro; Akutsu, Fua; Tani, Haruna; Akiyama, Takahiko.
Afiliação
  • Uchikura T; Department of Chemistry, Faculty of Science, Gakushuin University, 171-8588, 1-5-1, Mejiro, Toshima-ku, Tokyo, Japan.
  • Akutsu F; Department of Chemistry, Faculty of Science, Gakushuin University, 171-8588, 1-5-1, Mejiro, Toshima-ku, Tokyo, Japan.
  • Tani H; Department of Chemistry, Faculty of Science, Gakushuin University, 171-8588, 1-5-1, Mejiro, Toshima-ku, Tokyo, Japan.
  • Akiyama T; Department of Chemistry, Faculty of Science, Gakushuin University, 171-8588, 1-5-1, Mejiro, Toshima-ku, Tokyo, Japan.
Chemistry ; 30(33): e202400658, 2024 Jun 12.
Article em En | MEDLINE | ID: mdl-38600038
ABSTRACT
Photoinduced single-electron reduction is an efficient method for the mono-selective activation of the C-F bond on a trifluoromethyl group to construct a difluoroalkyl group. We have developed an electron-donor-acceptor (EDA) complex mediated single-electron transfer (EDA-SET) of α,α,α-trifluoromethyl arenes in the presence of lithium salt to give α,α-difluoroalkylarenes. The C-F bond reduction was realized by lithium iodide and triethylamine, two common feedstock reagents. Mechanistic studies revealed the generation of a α,α-difluoromethyl radical by single-electron reduction and defluorination, followed by the radical addition to alkenes. Lithium salt interacted with the fluorine atom to promote the photoinduced reduction mediated by the EDA complex. Computational studies indicated that the lithium-assisted defluorination and the single-electron reduction occurred concertedly. We call this phenomenon fluoride-coupled electron transfer (FCET). FCET is a novel approach to C-F bond activation for the synthesis of organofluorine compounds.
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Texto completo: 1 Base de dados: MEDLINE Idioma: En Revista: Chemistry Assunto da revista: QUIMICA Ano de publicação: 2024 Tipo de documento: Article País de afiliação: Japão

Texto completo: 1 Base de dados: MEDLINE Idioma: En Revista: Chemistry Assunto da revista: QUIMICA Ano de publicação: 2024 Tipo de documento: Article País de afiliação: Japão