Chemistry of silyl thioketones. Part 10. Synthesis and reactivity of α-silyl vinyl sulfides

Abstract

Aliphatic silyl thioketones containing an α-hydrogen atom undergo enethiolization to Z-α-silyl enethiols 2. Compounds 2 react with a variety of halides R³X to give open-chain α-silyl vinyl sulfides 3. Protiodesilylation of 3 was achieved upon treatment with fluoride ion to give vinyl sulfides 4. Reaction of 3 with Grignard reagents, in the presence of an appropriate nickel catalyst, results in a series of vinylsilanes 5 with a specific geometry.