Synthesis and Reactivity of Diethyl (Methylthio)(trimethylsilyl)methylphosphonate

Abstract

The title compound is obtained in 80% yield by silylation of the lithium salt of diethyl 1-methylthiomethylphosphonate. Other approaches involving sulfenylation of diethyl 1-trimethylsilylmethylphosphonate or the Arbuzov reaction of triethyl phosphite with bromo(methylthio)(trimethylsilyl)methane are less efficient. Aldehydes react with the lithium salt of diethyl (methylthio)(trimethylsilyl)methylphosphonate to give the corresponding 1-methylthioethenylphosphonates in good yields (60-85%) while the reaction with ketones is more complex and Peterson reaction products are formed in very low yields. Methylation, silylation, sulfenylation, and oxidation of the title compound are also described.