FLUORIDE CATALYZED REACTION OF SILYLACETYLENES WITH CARBONYL COMPOUNDS

Article abstract of DOI:10.1016/S0040-4020(01)88596-3

(Phenylethynyl)trimethylsilane undergoes nucleophilic addition to a variety of carbonyl compounds in the presence of a catalytic amount of fluoride anion to give silylated propargyl alcohol derivatives.The reaction fails with enolizable enones and cyclopentanone.The reaction of bis(trimethylsilyl)acetylene does not stop at the stage of monoadduct, and affords a considerable amount of symmetric bisadduct. (Trimethylsilyl)acetylene attacks 4-t-butylcyclohexanone from the axial side, as other metal acetylides do.Although much slower than the above cases, the reaction of alkynyltrimethylsilanes also proved successful.The reactivities of these (trimethylsilyl)-acetylenes are discussed in terms of the reaction mechanism and the nature of the reactive species, and also compared with those of the silylated enols under similar conditions.