Ozone Oxidation of Silylalkene: Mechanistic Study and Application for the Synthesis of Silacarboxylic Acid Derivatives

The
addition-type ozone oxidation of silylalkenes is a highly efficient
reaction to provide synthetically versatile α-silylperoxy carbonyl
compounds. To gain insight into the reaction mechanism, we performed
a computational study, which revealed that the reaction proceeds via
[1,2]-Brook rearrangement-type silyl migration of primary ozonide.
In sharp contrast to the addition-type reactions, the ozone oxidation
of α-alkoxysilylalkenes proceeds in a cleavage-type manner to
afford excellent yields of silacarboxylic acid esters via the 1,3-cycloelimination
of primary ozonide prior to 1,2-silyl migration.