Abstract: | Diarylamines in the benzob]thiophene series bearing electron donating or withdrawing groups, were prepared by Buchwald-Hartwig C-N coupling in moderate to high yields. The conditions used were Pd(OAc)2 (3 mol%), BINAP as ligand (4 mol%) and Cs2CO3 as base (1.4 equiv.), in toluene at 100°C, being 6-bromo or amino benzob]thiophenes coupled, respectively, with substituted anilines or phenylbromides. The 6-aminobenzob]thiophene derivatives were also prepared by palladium catalyzed C-N coupling of the corresponding 6-bromo compounds with benzophenone imine, followed by acidic hydrolysis of the imino derivatives. When 4-nitrobromobenzene and 4-bromobenzonitrile were used as coupling components, triarylamines were also isolated in small amounts. The presence of a fluorine atom on the phenylbromide highly increases the diarylamine yields. |