The invention of highly regioselective and stereoselective methods for the installation of carbon-heteroatom linkages remains a very active area of research. The interception of palladium π-allyl complexes with carbon nucleophiles is a well-established method for the construction of C-C bonds, but many opportunities remain for the analogous construction of C-O bonds. Our laboratory has a programmatic focus on the development of the di-tert-butyl-silanol auxiliary for alkene manipulation reactions. We envisioned a new method for the construction of C-O bonds via the intramolecular interception of a palladium π-allyl species with a pendant di-tert-butylsilanol functional group (Scheme 1). Based on our previous work as well as that of others, we expected such a reaction to be highly chemo-, regio-, and diastereoselective. This would be an important addition to existing technology for the synthesis of complex polyhydroxylated molecules (Scheme 1). Before undertaking reaction optimization, we first had to develop a method that would allow for facile access to the requisite starting materials (Scheme 2). Using our laboratory's silylation procedure, 3-butyn-1-ol or 4-pentyn-2-ol could be converted into the corresponding silanol. Bis-deprotonation with two equivalents of n-BuLi enabled condensation with a variety of aldehydes. Reduction of the alkyne to a cis-alkene was effected using Lindar's catalyst under 1 atm of H2 gas. Finally, the free alcohol was converted into an ethyl carbonate using ethyl chloroformate and pyridine. This procedure was remarkably modular, reproducible, and scalable. We have carried it out reliably on starting scales as large as 10 mmol, and all substrates shown in this account were prepared using this method.