Direct catalytic arylation of heteroarenes with -bromophenyl-substituted porphyrins.

The arylation of mono-, di- and tetra--bromophenyl-substituted porphyrins with the heteroarenes containing "acidic" C-H bonds, such as benzoxazole, benzothiazole and -methylimidazole was studied in the presence of three alternative catalytic systems: Pd(dba)/DavePhos/CsCO, Pd(PPh)/PivOH/KCO and Pd(OAc)/Cu(OAc)/PPh/KCO. The first catalytic system was found to be successful in the reaction with benzoxazole, the second one was less efficient for our purpose, while the third system proved to be most versatile and afforded corresponding mono-, di-, tri- and even tetraarylated derivatives of porphyrins.

Cu(I)-catalyzed N,N'-diarylation of natural diamines and polyamines with aryl iodides.

The Cu(I)-catalyzed N,N'-diarylation of natural diamines and polyamines such as putrescine, cadaverine, spermine, spermidine and their homologues is described. Aryl iodides bearing electron-donating and electron-withdrawing groups have been employed in the study. The CuI/2-(isobutyryl)cyclohexanone/DMF catalytic system has found to be more efficient in the diarylation of diamines and spermine while the CuI/L-proline/EtCN system proved to be preferable for the diarylation of other tri- and tetraamines like spermidine, norspermidine and norspermine.