Synthesis of phospholes and 1,1′-biphospholes mediated by zirconacyclopentadienes and PBr3

[Display omitted] •Highly efficient synthesis of phospholes through the reactions of Grignard reagents with in situ-generated 1-bromophospholes.•Easy substituent variation at the phosphorus atom of the phospholes.•Formation of 1,1′-biphospholes through Zn-promoted debromo-dimerization of 1-bromophospholes.•Gold-phosphole complexes serve as efficient catalysts in [3+2] cycloaddition of ynamides with 4,5-dihydro-1,2,4-oxadiazoles. The efficient synthesis of phospholes through the reactions of Grignard reagents with in situ-generated 1-bromophospholes has been developed. This method allows the easy substituent variation at the phosphorus atom of the phospholes. The 1,1′-biphospholes can also be conveniently prepared through Zn-promoted debromo-dimerization of 1-bromophospholes. The gold-phosphole complexes of LAuCl were also synthesized, which were found to act as efficient catalysts in gold-catalyzed [3+2] cycloaddition of ynamides with 4,5-dihydro-1,2,4-oxadiazoles.