%0 Journal Article
%A Bernardo, Olaya
%A González Pelayo, Silvia
%A Fernández López, Israel
%A López, Luis A.
%T Gold-catalyzed reaction of propargyl esters and alkynylsilanes: synthesis of vinylallene derivatives through a twofold 1,2- rearrangement
%D 2021
%U https://hdl.handle.net/20.500.14352/112664
%X The 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.
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