Fleming-Tamao oxidation

What is Fleming-Tamao oxidation?

In 1983 and 1984, Tamao and Fleming, respectively, reported a reaction that converts a silyl group into a hydroxyl group. This process is called oxidative desilylation and can be carried out using hydrogen peroxide or peracetic acid as an oxidant, and KF or KHF2 as an additive in Tamao’s procedure for di-isopropyl-methylalkylsilanes. Alternatively, a peroxy acid can be used as an oxidant under acidic conditions in Fleming’s procedure for phenyldimethylalkylsilanes. This reaction is commonly known as the Tamao-Fleming oxidation, or simply the Tamao oxidation.

Fleming-Tamao oxidation - general reaction scheme - Tamao-Fleming oxidation - Tamao oxidation
Fleming-Tamao oxidation
Fleming-Tamao oxidation - general reaction scheme - Tamao-Fleming oxidation - Tamao oxidation
Fleming-Tamao oxidation

Oxidative desilylation is an important method for the preparation of diols from cyclic silanes, especially in the case of dialkylsilanes, where two alcohols can be generated. This reaction has demonstrated its versatility and significance in modern organic synthesis. Organosilicon molecules can be easily prepared from the hydrosilylation of alkenes and alkynes with cis or trans stereochemistry, and alcohols or other derivatives can be obtained by the oxidative desilylation of the introduced silyl groups.

Although the phenyldimethylsilyl group can be converted into a hydroxyl group with retention of stereochemistry, it is not feasible to remove the trimethylsilyl group. However, allylsilanes may affect the stereochemistry retention of this reaction.

Overall, the Tamao-Fleming oxidation reaction has significant potential in organic synthesis, offering a useful and versatile method in the removal of silyl groups and alcohol preparations.

References

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