A variety range of functionalized aryl and heteroaryl zinc reagents were efficiently generated by using TMP2Mg· 2LiCl (TMP= 2, 2, 6, 6-tetramethylpiperamidyl) in the presence of ZnCl2. The subsequently functionalization gave after reaction with electrophiles the expected polyfunctionalized products in good yields. A detailed study concerned on the point how we found the protocol and how we optimized it was depicted.