Fleming–Tamao oxidation
| Fleming-Tamao oxidation | |
|---|---|
| Named after |
Ian Fleming Kohei Tamao |
| Reaction type | Organic redox reaction |
| Identifiers | |
| Organic Chemistry Portal | fleming-tamao-oxidation |
| RSC ontology ID | RXNO:0000210 |
The Fleming–Tamao oxidation, or Tamao–Kumada–Fleming oxidation, converts a carbon–silicon bond to a carbon–oxygen bond with a peroxy acid or hydrogen peroxide. Fleming–Tamao oxidation refers to two slightly different conditions developed concurrently in the early 1980s by the Kohei Tamao and Ian Fleming research groups.
The reaction is stereospecific with retention of configuration at the carbon–silicon bond. This allows the silicon group to be used as a functional equivalent of the hydroxyl group. Another key feature of the silicon group is that it is relatively stable due to the presence of the silicon atom, and therefore can tolerate various reaction conditions that the hydroxyl group can not tolerate. Due to the stability of the silicon group, organosilicon compounds are useful in the total synthesis of complex natural products and pharmaceutical drugs. For instance, the Fleming–Tamao oxidation has been used to accomplish the synthesis of subunits of tautomycin, an inhibitor that is used as a lead cancer compound and as an immunosuppressant.
In 1983, Tamao and co-workers were the first to report the successful transformation of an allyl alkoxy silyl to an allyl alcohol without an allylic shift. In their report, the chemists observed that the hydroxyl group was introduced exclusively onto the carbon atom to which the silicon atom was attached. In the same year, Tamao and group published another paper that showed that the carbon–silicon bond in alkoxy organosilicon compounds can be cleaved using H2O2 or m-CPBA under acidic, basic (chemistry), or neutral conditions, to afford the corresponding alcohols. A year later, Ian Fleming and group reported that the dimethylphenylsilyl (Me2PhSi) group can be converted to an hydroxyl group in a two-pot sequence. Later, in 1987, Fleming reported a one-pot variant to the two-pot sequence in which either bromine or mercuric ion acts as the electrophile. These early findings paved the way for the development of a large number of silicon-based reagents and the use of various silyl groups as functional equivalents of the hydroxyl group.
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