A novel and efficient access to polyfunctionnalized chiral 1-tetralols, bearing two contiguous quaternary carbon stereocenters, has been developed from various and easily accessible alkynyl-1,3-diketones, through a cascade process including a regioselective alkyne insertion, a 1,4-Rh shift, and a nucleophilic addition step via the desymmetrization of the 1,3-diketone moiety thanks to an appropriate rhodium-chiral diene complex in the presence of arylboronic acids.