6556-06-5Relevant articles and documents
FLUORIDE CATALYZED REACTION OF SILYLACETYLENES WITH CARBONYL COMPOUNDS
Kuwajima, I.,Nakamura, E.,Hashimoto, K.
, p. 975 - 982 (2007/10/02)
(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.
The reaction of some propargyl alcohols with benzeneselenenyl chloride
Garratt, Dennis G.,Beaulieu, Pierre L.,Morisset, Veronique M.
, p. 927 - 934 (2007/10/02)
The reaction of benzeneselenenyl chloride with twenty-two propargyl alcohols in methylene chloride solution is reported.Products of both Markownikoff and anti-Markownikoff regiochemistry are formed in an anti stereospecific manner.The regioselectivity or specificity is found to be very dependent upon the nature of the substituents geminal to the alcoholic moiety.In general the presence of bulky substituents geminal to the alcoholic moiety tend to favour formation of the anti-Markownikoff adduct under conditions of kinetic control.The Markownikoff adducts are found to be favoured thermodynamically.