Transition metal-catalyzed reactions are atom economical and environmentally benign processes, which make them superior to traditional stoichiometric reactions. Transition metal-catalyzed carbonylation reactions of unsaturated systems has become an important methodology for the synthesis of carbonyl containing synthetically valuable compounds. One of these types of reactions is the alkoxycarbonylation of unsaturated systems over transition metals in the presence of alcohol and under CO atmosphere (Scrivanti, et. al. 1998). Pionering works on palladium-catalyzed alkoxycarbonylation of allylic and propargylic systems with a leaving group at an apropriate positions leading to β,γ-unsaturated and allene esters, respectively have been established by several research groups (Tsuji, et al. 2004). Recently, Artok and co-workers developed new methods for the construction of functionalized vinylallene esters via palladium-catalyzed alkoxycarbonylation of 2,4-enyne carbonates (Akpınar, et al. 2011). After tuning the reaction conditions precisely, the methodology could be improved to allow a high degree of center-to-axial chirality transfer (Karagöz, et al. 2014). Within the context of this study, palladium-catalyzed alkoxycarbonylative 1,5-substitution of conjugated enyne oxiranes was also found to provide a diastereoselective route to (E)-configured 7-hydroxy-2,3,5-trienoates. The reactions proceeded in a highly stereoselective manner, possibly through sequential formation of -allylpalladium and -vinylallenyl palladium complexes. The major diastereomeric form of the product was determined by the configuration of the alkenyl moiety of the substrate.