An efficient stereo-controlled synthesis of enyne and enediyne derivatives, via sequential Suzuki-Miyaura coupling reactions from easily prepared 1-alkene-1,2-diboronic esters and alkynyl bromides, is reported. The resulting enyne boronic esters were subjected to Borono-Mannich and Suzuki coupling reactions independently to obtain α,β-unsaturated aminoester and tri-substituted olefin derivatives, respectively. Additionally, divergent syntheses of triazole and cyclopropylboronate derivatives are also reported.