Summary: The Zr-catalyzed carboalumination of propargyl and homopropargyl derivatives containing OH, OSiMe2Bu-t, SPh, or I provides, in a highly stereo-and regioselective manner, the corresponding (E)-(Bmethyl-alkenyl) dimethylalkanes, which are convertible to various difunctional trisubstituted (E)-alkene synthons.