Stereoselective synthesis of tetrasubstituted alkenes is a challenging problem in chemical synthesis. New protocols to access this important, yet simple, structural motif are of fundamental significance because they are found in many valuable molecules and can be utilized in a variety of important complexity building chemical transformations. The two-step strategy presented herein involves stereoselective generation of an alkenyl pseudohalide followed by a stereospecific metal-catalyzed cross-coupling.