Silyl enol ethers are important synthetic intermediates that are used in a variety of reactions. The ozonolysis of silyl enol ethers to anomalous 1,2-dioxolane products has not yet been fully been explored. Though the synthesis of silyl enol ethers from aldehydes, ketones, and esters is relatively straightforward, the most commonly used methods still require air- or moisture-sensitive conditions and/or the use of toxic solvents. We have shown that silyl enol ethers can be easily synthesized from aldehydes and ketones under mild conditions and with a straightforward workup procedure in good to excellent yields. We ozonolyzed these silyl enol ethers to study their reactivity and found that unsubstituted and 1-substituted silyl enol ethers gave (3-alkyl)-3-silyloxy1,2-dioxolane products in excellent to moderate yields, respectively. However, alkyl substitution at the 2-position led to the formation of polymeric product. Finally, we investigated the reactions of these dioxolane products and found that they can undergo rearrangement to β-hydroxy esters via the addition of acid and diols via hydrogenation.
Wilson, K. (2015). Ozonolysis of silyl enol ethers: Synthesis of 3-silyloxy-1,2-and 3-alkyl-3-silyloxy-1,2-dioxolanes (Undergraduate honors thesis, University of Redlands). Retrieved from http://inspire.redlands.edu/cas_honors/123