Bernardo, OlayaGonzález Pelayo, SilviaFernández López, IsraelLópez, Luis A.2024-12-162024-12-162021-09-28Bernardo O, González-Pelayo S, Fernández I, López LA. Gold-Catalyzed Reaction of Propargyl Esters and Alkynylsilanes: Synthesis of Vinylallene Derivatives through a Twofold 1,2-Rearrangement. Angew Chem Int Ed Engl. 2021 Nov 22;60(48):25258-25262. doi: 10.1002/anie.202110783. Epub 2021 Oct 21. PMID: 34581473; PMCID: PMC9298039.10.1002/anie.20211078https://hdl.handle.net/20.500.14352/112664The reaction of propargyl esters with alkynylsilanes under gold catalysis provides vinylallene derivatives through consecutive [1,2]-acyloxy/[1,2]-silyl rearrangements. Good yields, full atom-economy, broad substrate scope, easy scale-up and low catalyst loadings are salient features of this novel transformation. Density Functional Theory (DFT) calculations suggest a reaction mechanism involving initial [1,2]-acyloxy rearrangement to generate a gold vinylcarbene intermediate which upon regioselective attack of the alkynylsilane affords a vinyl cation which undergoes a type II-dyotropic rearrangement involving the silyl group and the metal fragment. Preliminary results on the enantioselective version of this transformation are also disclosed.engAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/journal articlehttps://doi.org/10.1002/anie.202110783https://onlinelibrary.wiley.com/doi/full/10.1002/anie.202110783open access547AlkynylsilanesAllenesCarbenesGoldRearrangementsQuímica orgánica (Química)2306 Química Orgánica