%0 Generic
%A Ferguson, Devin
M.
%A Bour, James R.
%A Canty, Allan J.
%A Kampf, Jeff W.
%A Sanford, Melanie S.
%D 2017
%T Stoichiometric and Catalytic Aryl–Perfluoroalkyl Coupling at Tri-tert-butylphosphine Palladium(II) Complexes
%U https://acs.figshare.com/articles/dataset/Stoichiometric_and_Catalytic_Aryl_Perfluoroalkyl_Coupling_at_Tri-_i_tert_i_-butylphosphine_Palladium_II_Complexes/5305447
%R 10.1021/jacs.7b05216.s002
%2 https://acs.figshare.com/ndownloader/files/9112957
%K Pd
%K CF 2 CF 3
%K II
%K CF 2 CF 3 ligand
%K TMSCF 2 CF 3
%K DFT
%K CF 3 analogue
%K side products limits
%K CF 3
%K α- fluoride elimination
%X This 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.
%I ACS Publications