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The silapinacol rearrangement: Conversion of α,β-dihydroxysilanes into α-silyl carbonyl compounds

✍ Scribed by Robert F Cunico

Publisher
Elsevier Science
Year
1986
Tongue
French
Weight
186 KB
Volume
27
Category
Article
ISSN
0040-4039

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✦ Synopsis

Treatment of cc,+dihydroxysilanes with trifluoroacetic acid in chloroform results in a 1,2-migration of the silyl group to give a-silyl aldehydes and ketones. The t-butyldimethylsilyl compounds can be isolated in high yields.

Several workers' have reported that a,@-dihydroxytrimethylsilanes (1, R = Me) are converted to desilylated carbonyl compounds (4) under the influence of protonic acids, a process which has generally been considered to proceed via b-elimination (path a) of a protonated intermediate (2). We wish to present evidence that, at least under certain conditions, this process instead follows the sequence indicated by path b, wherein loss of water from the beta-site is accompanied2 by a 1,2-silyl group migration ("silapinacol rearrangement") 3 to afford the intermediate 3. This may then suffer subsequent desilylation to generate the observed carbonyl compound 4, 4 H+ -HOH ;c b SiR3 SiR3

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