Synthesis of a-Silyl Esters and Reactivities of the Si-C Bond on Methanolysis

Abstract

α-Silyl ester has been known to be specific silicon compound because of the easiness of the Si-C bond cleavage under mild conditions. In this investigation, various silyl esters were prepared and allowed to react with methanol.
Consequently, the following substituent effects of R¹, R² in R¹Me₂SiCH₂CO₂R² on the reactivity with methanol have been revealed:
(1) the Si-C bond cleavage are accelerated by electronwithdrawing substituents,
(2) methanolysis is inhibited by bulky substituents presumably due to the stereochemical effect,
(3) reactivity: R¹Me₂SiCH₂CO₂R²
R¹: H >C1CH ₂ > Ph >CH₂=CH > Me > n-Pr>n-C₃H₁₇ >i-Pr
R²: Ph>Me>Et>n-C₈H₁₇