ja7b05216_si_002.cif (1.04 MB)
Stoichiometric and Catalytic Aryl–Perfluoroalkyl Coupling at Tri-tert-butylphosphine Palladium(II) Complexes
Version 3 2017-08-17, 14:49
Version 2 2017-08-16, 17:05
Version 1 2017-08-11, 20:03
dataset
posted on 2017-08-11, 00:00 authored by Devin
M. Ferguson, James R. Bour, Allan J. Canty, Jeff W. Kampf, Melanie S. SanfordThis 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.