Selective Metallation of 3-Halothiophenes: Practical Methods for the Synthesis of 2-Bromo-3-formylthiophene

Selective lithiation of 3-bromothiophene was accomplished under controlled conditions without formation of undesired thienyllithium compounds. A thienyl Grignard reagent derived from 2-bromo-3-iodothiophene was transformed into 2-bromo-3-formylthiophene in high selectivity by formylation with dimethylformamide (DMF) at optimal reaction temperature.