On the basis of our observation that (E)-1-bromo-1-alkenes undergo preferentially stereospecific Pd-catalyzed cross-couplings with a variety of organometallics, in the presence of the corresponding (Z)-stereoisomers, efficient and convenient diastereoselective procedures have been developed to prepare nearly stereoisomerically pure (E)-1-trimethylsilyl-2-alkenes (4),(E)-1-trimethylsilyl-1-alken-3-ynes (5),(1E, 5E)-1- ...