Silyl peroxide rearrangement

This excellent method of oxidative cleavage (/) of carbon-silicon bonds requires that the silane carry an electronegative substituent (2), such as alkoxy or fluoro. Either hydrogen peroxide or mcpba may be used as oxidant, and the alcohol is produced with retention of configuration (3). Fluoride ion is normally a mandatory additive in what is believed to be a fluoride ion-assisted rearrangement of a silyl peroxide, as shown below ... 

ALLYLIC REARRANGEMENT Bis(trimethyl-silyl)peroxide-Vanadyl acetylacetonate. 

The rearrangement 12 13 is not straightforward and two alternatives routes have been suggested. One of them involves a 1,3 transfer from silicon to oxygen to give the silyl radical 15 followed by Sui reaction on the peroxide moiety [15]. The other indicated by PM3 calculations is a dioxirane-like three-membered intermediate 16 having a pentacoordinated central silicon followed by a 1,2 silyl migration to afford radical 13 [19]. 

A number of examples of intramolecular rearrangements of organometallic and organometalloidal peroxides are well known, and there are several instances indicating a strong tendency for substituted silyl groups to undergo... 

Brook, A. G., Macrae, D. M. 1,4-Silyl rearrangements of siloxyalkenes to siloxyketones during peroxidation. J. Organomet. Chem. 1974, 77, C19-C21. 

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