We present full details of our new methods for preparing functionalized benzynes with lithium di-alkyl (2, 2, 6, 6-tetramethylpiperidino) zincate (R2Zn (TMP) Li) through deprotonative zincation as a key reaction. In this system, by choosing appropriate ligands for the zincate, either regioselective zincation of functionalized haloaromatics or the generation of substituted benzynes can be controlled in good yields with excellent chemoselectivity, ...