[reaction: see text] 2-Triethylsiloxy-substituted 1,3-butadiene has been prepared in gram quantities from chloroprene via a simple synthetic procedure. Silatrane and catechol-substituted analogues of this main group element substituted diene were prepared by ligand exchange and characterized by X-ray crystallography in addition to standard spectroscopic techniques. Diels-Alder reactions of these dienes are reported as well as subsequent TBAF assisted/Pd-catalyzed Hiyama cross-coupling reactions of those Diels-Alder adducts.