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...
moreThe 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(PPh3)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.