Selective deprotonation of tetra[3,4]thienylene in the presence of n-BuLi

The sequential lithiation mechanism for the selective deprotonation of tetra[3,4]thienylene (1) to form Li4-1 in the present of n-BuLi in THF is investigated. The specific contralateral and ipsilateral selectivities of the lithiation sites in the different steps are explored. A series of tetra-substituted 1 are obtained, viaLi4-1 with electrophiles, in good yields.