Abstract
The Suzuki reaction of tetrabromothiophene with arylboronic acids provides a regioselective approach to various 5‐aryl‐2,3,4‐tribromothiophenes, symmetrical 2,5‐diaryl‐3,4‐dibromothiophenes, and tetraarylthiophenes. Unsymmetrical 2,5‐diaryl‐3,4‐dibromothiophenes are prepared by Suzuki reaction of 5‐aryl‐2,3,4‐tribromothiophenes. Tetraarylthiophenes containing two different types of aryl groups are obtained by Suzuki reactions of 2,5‐diaryl‐3,4‐dibromothiophenes. During the optimization of the conditions of each individual reaction, the solvent, the catalyst and the temperature play an important role. In several cases, classical conditions [use of tetrakis(triphenylphosphane)palladium(0), Pd(PPh~3~)~4~, as the catalyst] gave excellent yields. The yields of those transformations which failed or proceeded sluggishly could be significantly improved by application of a new biarylmonophosphine ligand developed by Buchwald and co‐workers. Regioselective metal‐halide exchange reactions of tetrabromothiophene provide a convenient approach to various 2,5‐disubstituted 3,4‐dibromothiophenes. 5‐Alkyl‐2‐trimethylsilyl‐3,4‐dibromothiophenes could be prepared in one pot by sequential addition of trimethylchlorosilane and alkyl bromides. The reaction of tetrabromothiophene with methyl chloroformate and subsequent Suzuki reactions afforded 3,4‐diaryl‐2,5‐bis(methoxycarbonyl)thiophenes.