Paul F. Hudrlik

Preparation of Silylated Esters, Lactones, and Amides

Abstract We have recently found β-ketosilanes (α-trimethylsilyl ketones) to be useful precursors to β-hydroxyalkylsilanes, which are readily converted to olefins.2 α-Silyl esters have been shown to be useful precursors to α,β-unsaturated esters.3 In connection with our interest in the use of α-silylated carbonyl compounds in organic synthesis, we have investigated the possibility of preparing these compounds by silylation of enolates and by alkylation of silylated carbonyl compounds.4 In several cases, the C-silylated products can be obtained in good yields.

Preparation of a Trans α,β-Epoxysilane by Selective Pyrolysis

Abstract α,β-Epoxysilanes have been shown to be useful synthetic intermediates2 for the preparation of carbonyl compounds3 and stereoisomerically-pure olefins4 and heteroatom-substituted olefins5 (vinyl bromides,5 enol acetates,5 enol ethers,5 enamides,5 and vinyl mesylates6). In many of their reactions, α,β-epoxysilanes serve as stereospecific vinyl cation equivalents;4–6 therefore methods to prepare stereoisomerically-pure α,β-epoxysilanes are of considerable importance. Although other methods for preparing α,β-epoxysilanes have recently been developed,7 the only general method for preparing stereoisomerically-pure α,β-epoxysilanes is epoxidation of the corresponding vinylsilanes.