Corey-Gilman-Ganem oxidation

What is Corey-Gilman-Ganem oxidation?

The Corey-Gilman-Ganem oxidation, first reported by Corey and colleagues in 1968, is an efficient method for synthesizing α,β-unsaturated esters from α,β-unsaturated aldehydes or allyl alcohols using manganese dioxide and potassium cyanide in an appropriate alcohol solvent. This reaction is also known as the Corey-Ganem oxidation.

Corey-Gilman-Ganem oxidation - Corey-Ganem oxidation - general reaction scheme
Corey-Gilman-Ganem oxidation

While manganese dioxide MnOis typically a mild oxidant that converts primary allylic alcohols into conjugated aldehydes without further oxidation to carboxylic acids, the addition of HCN and cyanide allows for the conversion of α,β-unsaturated aldehydes into cyanohydrins, which can be oxidized by MnO2 to form acyl cyanides. In the presence of an alcohol, this reaction produces α,β-unsaturated esters. It is worth noting that this reaction only works with α,β-unsaturated aldehydes and does not cause any cis-trans isomerization of the α,β-unsaturated double bond.

References

New methods for the oxidation of aldehydes to carboxylic acids and esters
Elias J. Corey, Norman W. Gilman, and B. E. Ganem
Journal of the American Chemical Society 1968 90 (20), 5616-5617
DOI: 10.1021/ja01022a059

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