1,2-(Bis)trifluoromethylation of Alkynes: A One-Step Reaction to Install an Underutilized Functional Group.

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  • Author(s): Guo S;Guo S; AbuSalim DI; AbuSalim DI; Cook SP; Cook SP
  • Source:
    Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2019 Aug 19; Vol. 58 (34), pp. 11704-11708. Date of Electronic Publication: 2019 Jul 11.
  • Publication Type:
    Journal Article; Research Support, N.I.H., Extramural
  • Language:
    English
  • Additional Information
    • Source:
      Publisher: Wiley-VCH Country of Publication: Germany NLM ID: 0370543 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1521-3773 (Electronic) Linking ISSN: 14337851 NLM ISO Abbreviation: Angew Chem Int Ed Engl Subsets: MEDLINE
    • Publication Information:
      Publication: <2004-> : Weinheim : Wiley-VCH
      Original Publication: Weinheim/Bergstr. : New York, : Verlag Chemie ; Academic Press, c1962-
    • Subject Terms:
      Alkenes/*chemistry ; Alkynes/*chemistry ; Copper/*chemistry ; Hydrocarbons, Fluorinated/*chemistry; Catalysis ; Methylation ; Molecular Structure ; Oxidation-Reduction
    • Abstract:
      Modifying the electronic properties of olefins is the quintessential approach to tuning alkene reactivity. In this context, the exploration of trifluoromethyl groups as divergent electronic modifiers has not been considered. In this work, we describe a copper-mediated 1,2-(bis)trifluoromethylation of acetylenes to create E-hexafluorobutenes (E-HFBs) under blue light in a single step. The reaction proceeds with high yield and E/Z selectivity. Since the alkyne captures two trifluoromethyl groups from each molecule of bpyCu(CF 3 ) 3 , mechanistic studies were conducted to illuminate the role of the reactants. Interestingly, E-HFBs exhibit remarkable stability to standard olefin functionalization reactions in spite of the pendant trifluoromethyl groups. This finding has significant implications for medicine, agroscience, and materials.
      (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
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    • Grant Information:
      R01 GM121840 United States GM NIGMS NIH HHS
    • Contributed Indexing:
      Keywords: alkynes; copper; difunctionalization; persulfate; trifluoromethylation
    • Accession Number:
      0 (Alkenes)
      0 (Alkynes)
      0 (Hydrocarbons, Fluorinated)
      789U1901C5 (Copper)
    • Publication Date:
      Date Created: 20190618 Date Completed: 20200911 Latest Revision: 20231113
    • Publication Date:
      20240829
    • Accession Number:
      PMC7065645
    • Accession Number:
      10.1002/anie.201905247
    • Accession Number:
      31206968