Herein, we present a novel method for the double allylic substitution of alkenyl-vic-diols, employing dual catalysis (Lewis acid/transition metal). This approach enables the introduction of two distinct nucleophiles, providing direct access to complex molecular scaffolds. At the outset of the work, we screened conditions for the first allylic substitution. Although many Lewis acids promoted the reaction, BF3•Et2O proved superior to every other catalyst (see the supplementary information for detailed optimization). Moreover, the two sequential substitution reactions could be achieved in one-pot by simply adding [Pd(allyl)Cl]2, XantPhos, and a THF solution of sodium dimethylmalonate as the second nucleophile. The reaction proceeded well for the formation of variously substituted tetrahydrofuran products (Scheme 2). In particular, the reaction benefited from a Thorpe-Ingold effect (2a-2d). Even sterically demanding tertiary alcohols performed well as nucleophiles. The reaction could be applied to the synthesis of tetrahydropyran 2f, although with lower yield. Finally, other Onucleophiles such as phenol and carboxylic acid also proceeded (2g, 2h). Remarkably, the lactone functionality in 2h was not affected during the subsequent Tsuji-Trost reaction. The first substitution was not limited to the formation of new C-O bonds. Indeed, various protected amines could be employed, leading to the formation of pyrrolidine derivatives 2i-2l having Ts, Ac, Boc and Tf protecting groups on the amino functionality. Moreover, using indoles as nucleophiles the tetrahydrocarbazole product 2m was obtained in excellent yield. Finally, a C-S bond could also be forged using a thiol as the nucleophile, leading to tetrahydrothiophene 2n. Scheme 2. Scope of nucleophiles for the first allylic substitution. Reactions were carried out using 1 (0.2 mmol), trimethyl orthoacetate (0.3 mmol), BF3•Et2O (0.04 mmol) in DCM, then [Pd(allyl)Cl]2 (0.01 mmol), XantPhos (0.02 mmol) and a solution of sodium malonate (0.4 mmol in 1 mL THF) were added in the same pot.