“…Following these seminal reports, Paton and Maseras proposed, based on DFT calculations, that the regioselectivity observed by Widenhoefer and Yamamoto is due to isomerisation of the kinetic tertiary allylic ether 3 to the thermodynamic primary allylic ether 2 , rather than preferential activation of 1 at the less‐hindered double bond, as originally assumed (reaction (2), Scheme ) . Drawing on previous success in controlling the regioselectivity of gold‐catalysed alcohol additions to cyclopropenes, we subsequently developed conditions to suppress isomerisation of 3 to 2 , thereby switching the regioselectivity to the kinetic, tertiary allylic ether product 3 (reaction (3), Scheme ) . The use of DMF as solvent was the crucial difference, possibly because it reduces the activity of the active cationic gold catalyst (IPr)Au + (IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene) by means of reversible coordination …”