Abstract
Aryl triflates are selected as suitable electrophile coupling partners for the phosphorus-directed
rhodium(III)-catalyzed direct C–H arylation of polyaromatic phosphines. We report
herein simple conditions for the peri-C–H functionalization of polyarylphosphines, where a [Rh(III)Cl2Cp*]2 precatalyst is employed to provide a convenient access to polyarylated phosphines
in up to 93% isolated yield. This synthetic approach tolerates a wide range of different
aryl trifluoromethylsulfonate derivatives bearing either electron-donating (COMe,
CN, CF3 or Cl) or electron-withdrawing substituents (Me, OMe) at the para-, meta- and ortho-positions, and includes bulky polyaromatic triflate substrates. We further describe
access to a large class of polycyclic aromatic hydrocarbon phosphine ligands, their
oxidized derivatives (i.e., their oxides and selenides), their coordination modes
with Au(I) and Cu(I) coinage metal salts, and their use as efficient ligands for the
atom-economic, gold-catalyzed oxidative cyclization of terminal alkynes with nitriles.
Key words
arylation - catalysis - P-ligand directed C–H activation - rhodium - trifluoromethylsulfonates
- oxazoles
