Aryl Triflates in Phosphorus-Directed Rhodium(III)-Catalyzed C–H Activation

Abstract

Aryl triflates were selected as suitable electrophile coupling partners for the P-directed rhodium(III) catalyzed direct C–H arylation of polyaromatic phosphines. We report herein simple conditions in the peri-C–H functionalization of polyarylphosphines, where the [Rh(III)Cl2Cp*]2 precatalyst is employed to provide a convenient access to polyarylated phosphines, up to 93% isolated yield. Our synthetic approach tolerates a scope of different aryl trifluoromethyl sulfonate derivatives bearing either electron-donating (COMe, CN, CF3 or Cl) or electron-withdrawing substituents (Me, OMe) that are present in para-, meta- and ortho-position, and includes bulky polyaromatic triflate substrates. We further described the access to a large class of PAH phosphine ligands, their oxidized derivatives (both from Se- and O-reaction), their coordination mode with Au(I) and Cu(I) coinage metal salts, and their use as efficient ligands in the atom-economic gold-catalyzed oxidative cyclisation of terminal alkynes with nitriles.