Nickel and palladium catalyzed C−H trifluoromethylation using trifluoromethyliodide: investigations into new reactivity

Nicholas S. D. Solomon, Mohan Bhadbhade, Ruoming Tian, Sinead T. Keaveney*

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

    3 Citations (Scopus)
    59 Downloads (Pure)

    Abstract

    Due to the prevalence of the trifluoromethyl group (CF3) in high-value organic compounds, there is a constant demand for more selective, efficient and economical trifluoromethylation strategies. In this report we present detailed experimental and computational investigations into the use of cheap and atom-economical CF3I in transition metal catalyzed trifluoromethylation. The mechanistic insight gained allowed novel C−H trifluoromethylation processes to be developed, using both palladium and nickel catalysis. The reported methodology is remarkably selective for C−H trifluoromethylation, with substituents such as amino, nitro, bromo and aldehydes tolerated. Our experimental and computational studies suggest that radical species are not involved, and that the key C−H activation step is facilitated by an unusual difluorocarbene intermediate. Importantly, arylCF3 formation occurs through unique arylCF2-F based reductive elimination, likely from Pd(II)/Ni(II) but potentially through oxidatively-induced reductive elimination from Pd(IV)/Ni(IV). This is the first example of nickel-mediated trifluoromethylation where reductive elimination from nickel can occur in a catalytic manner.

    Original languageEnglish
    Article numbere202200918
    Pages (from-to)1-10
    Number of pages10
    JournalChemCatChem
    Volume14
    Issue number20
    Early online date18 Aug 2022
    DOIs
    Publication statusPublished - 21 Oct 2022

    Bibliographical note

    Copyright the Author(s) 2022. Version archived for private and non-commercial use with the permission of the author/s and according to publisher conditions. For further rights please contact the publisher.

    Keywords

    • C−H activation
    • difluorocarbene
    • nickel
    • palladium
    • trifluoromethylation

    Fingerprint

    Dive into the research topics of 'Nickel and palladium catalyzed C−H trifluoromethylation using trifluoromethyliodide: investigations into new reactivity'. Together they form a unique fingerprint.

    Cite this