The Fleming–Tamao oxidation is a reaction that converts silanes into alcohols using peracids or hydrogen peroxide. The reaction is named after Kohei Tamao and Ian Fleming, who independently reported slightly different versions of this transformation in 1983 and 1984, respectively.

• Reagents: Hydrogen peroxide or peracid, solvent, fluorinated additives

• Reactants: Silanes

• Products: Alcohols

• Reaction Type: Oxidation reaction

Experimental Tips:

• The reaction is stereospecific—the configuration of the carbon–silicon bond is retained during oxidation.

• The trimethylsilyl group is non-polar and relatively unreactive, making it compatible with many reagents and conditions that would not tolerate free alcohols. This allows its use without requiring hydroxyl protection during synthesis.

• Increasing the steric bulk around the silicon center usually slows the reaction rate. In some cases, large substituents (e.g., tert-butyl) can completely inhibit the reaction. Smaller groups (e.g., methyl, ethyl) are more favorable for oxidation.

Reaction Mechanism

Fleming Oxidation Mechanism

Tamao Oxidation Mechanism

Key References:

• Original Publications

  • Fleming, I.; Henning, R.; Plaut, H. E. J. Chem. Soc., Chem. Commun., 1984, 1, 29–31.

  • Tamao, K.; Ishida, N.; Tanaka, T.; Kumada, M. Organometallics, 1983, 2(11), 1694–1696.

• Notable Citations

  • Synthesis of a C1–C21 Subunit of the Protein Phosphatase Inhibitor Tautomycin: A Formal Total Synthesis, J. Org. Chem., 2001, 66(4), 1373–1379.

  • Fleming–Tamao Oxidation and Masked Hydroxyl Functionality: Total Synthesis of (+)-Pramanicin and Structural Elucidation of the Antifungal Natural Product (−)-Pramanicin, J. Org. Chem., 1999, 64(16), 6005–6018.

  • Rhodium-Catalyzed Regioselective Silylation of Alkyl C–H Bonds for the Synthesis of 1,4-Diols, J. Am. Chem. Soc., 2018, 140, 1460–1470.