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Stoichiometric and catalytic aryl-perfluoroalkyl coupling at tri-tert-butylphosphine palladium(II) complexes
journal contribution
posted on 2023-05-19, 10:48 authored by Ferguson, DM, Bour, JR, Allan CantyAllan Canty, Kampf, JW, Sanford, MSThis Communication describes studies of Ph–RF (RF = CF3 or CF2CF3) coupling at Pd complexes of general structure (PtBu3)PdII(Ph)(RF). The CF3 analogue participates in fast Ph-CF3 coupling (<5 min at 80 °C). However, the formation of side products limits the yield of this transformation as well as its translation to catalysis. DFT and experimental studies suggest that the side products derive from facile α-fluoride elimination at the 3-coordinate PdII complex. Furthermore, they show that this undesired pathway can be circumvented by changing from a CF3 to a CF2CF3 ligand. Ultimately, the insights gained from stoichiometric studies enabled the identification of Pd(PtBu3)2 as a catalyst for the Pd-catalyzed cross-coupling of aryl bromides with TMSCF2CF3 to afford pentafluoroethylated arenes.
History
Publication title
Journal of the American Chemical SocietyVolume
139Issue
34Pagination
11662-11665ISSN
0002-7863Department/School
School of Natural SciencesPublisher
American Chemical SocietyPlace of publication
1155 16Th St, Nw, Washington, USA, Dc, 20036Rights statement
Copyright 2017 American Chemical SocietyRepository Status
- Restricted