Gold (I) and (III) salts have been found to be highly effective at the catalysis of ether formation from alcohols. Intramolecular ether formation of a 1, 5-diol was also achieved, with a stereoselectivity that indicates that an SN1 mechanism predominates. In an attempt to form a seven-membered ring, a stable 14-membered dimer product was also formed. Attempts to control the diastereoselectivity of the reaction using a chiral anionic counterion did not ...