Journal of Organic Chemistry p. 691 - 693 (1981)
Update date:2022-08-03
Topics:
Washburne, Stephen S.
Szendroi, Robert
Ten acylic, cyclic, and aralkyl-type silanes were treated with triphenylcarbenium tetrafluoroborate in dichloromethane to measure rates of oxidative desilylation: RCH2CH2SiR3+Ph3C(1+)BF4(1-)->Ph3CH+RCH=CH2+R3SiF+BF3.The divergence of rates, from Ph2CHCH2SiMe3, which was inert, through dimethylsilacyclopentane (k2=4E-6), to dimethylsilacyclohexane (k2=2.2E-3), can not be rationalized on purely electronic grounds.A transition state requiring anticoplanar arrangement of the silicon moiety and β-hydrogen to be extruded is proposed.Dimethylsilacyclobutane, which reacts extremely rapidly (k2 approx. 2E-2), suffers allylic cleavage of the initially formed fluoro(2-propenyl)dimethylsilane.As the olefin products suffer decomposition or polymerization under the reaction conditions, this desilylation is of minimal preparative value.
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