Several bicyclic compounds bearing a 1,2-cyclopentanediol have been prepared from various anti- or syn-gamma-bromopropargylic diols and cis-dioxolanes under palladium(0) catalysis. The reaction proceeds through a 5-exo-dig cyclocarbopalladation. When the corresponding trans-dioxolanes are used, the only products isolated are obtained from a direct Stille cross-coupling reaction. [reaction: see text]