Synthesis of α,β-Unsaturated Acylsilanes via Perrhenate-Catalyzed Meyer-Schuster Rearrangement of 1-Silyialkyn-3-ols

We report the synthesis of alpha,beta-unsaturated acylsilanes via the perrhenate-catalyzed Meyer-Schuster rearrangement of 1-silylalkyn-3-ols. Propargylic alcohols derived from TES-acetylene and substituted benzaldehydes can be converted to acylsilanes using a combination of p-TSA. H2O and n-Bu4N center dot ReO4, or Ph3SiOReO3 in good yields. Some propargylic alcohols derived from ketones, as well as aliphatic and unsaturated aldehydes, can also be converted to acylsilanes; however, they were often prone to side reactions.