Fleming-Tamao Oxidation
The Fleming-Tamao oxidation allows the transformation of carbon-silicon bonds to the corresponding carbon-oxygen bonds.
General features: 1. Carbon-silicon bonds can be introduced stereospecifically. For example, via the regioselective transition metal-catalyzed hydrosilylation of olefins. 2. The silicon atom does not have lone pairs of electrons, so it does not coordinate with electrophiles or Lewis acids. 3. The oxidation conditions are mild enough to tolerate a wide range of functional groups. 4. The isolation of the product alcohol is straightforward since the by-products of the oxidation are usually water-soluble.
Fleming-Tamao Oxidation
Reaction Mechanism
1. SEAr by the electrophile on the phenyl ring. 2. Attack of the heterosilane by the peroxide gives a silyl peroxide. 3. [1,2]-alkyl shift affords an alkoxysilane. 4. Hydrolysis to the desired alcohol.
Experimental Procedure
A vial is charged with the substrate (0.17 mmol, 1.0 eq) and AcOOH (30% in aqueous AcOH, 3.4 mL). To this solution is added Hg(OAc)2 (2.0 eq) in a single portion. The reaction is stirred 45 min at 23 °C. The reaction mixture is diluted with EtOAc and pipetted over an ice-cold mixture of sat. aq. Na2S2O3 and saturated, aqueous NaHCO2 (1:4). This aqueous solution is then extracted with EtOAc and CHCl3/i-PrOH (3:1). The organic extracts are combined and dried over Na2SO4, filtered, and concentrated under reduced pressure to afford a crude solid which is purified by flash chromatography to afford the desired product (55% yield).
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