CÀ H arylation of 1-pyrenylphosphine derivatives catalyzed by rhodium and directed by a diphenylphosphino group is selectively achieved at the K-region, i. e. 4-, 5-, 9-, or 10-position of the pyrene moiety. This peri CÀ H activation/arylation of pyrenes using (hetero)aryl bromide coupling partners tolerates both electron-donating and electron-withdrawing groups on the arene, and provides isolated yields of products between 25% to 90%, including from bulky polyaromatic bromoarene substrates. We achieved investigations directed at the formation and reactivity of pertinent intermediate species in this CÀ H arylation reaction. The P-ligand coordination at rhodium was established using 31 P NMR and XRD analysis, and we isolated five-membered rhodacycles as intermediates to the directed CÀ H functionalization. The data obtained overall supported the occurrence of a cationic rhodium catalytic process. We further described the access to a large class of pyrenylphosphine ligands and their selenated derivatives. Phosphine selenation allows to rapidly estimate from 1 J P = Se values the basic character of the ligand in the perspective of their use for coordination. Accordingly, linear P-coordinated Au(I) gold complexes were isolated, in addition to the variously coordinated Rh(III) complexes. The present methodology significantly extends the scope of polyaromatics that are functionalizable at the K-Region by direct CÀ H activation, beyond smaller-sized naphtalenes and aminopyrenes.
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.
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