organic chemistry Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, ...

, the Ganem oxidation is a

name reaction A name reaction is a chemical reaction named after its discoverers or developers. Among the tens of thousands of organic reactions that are known, hundreds of such reactions are well-known enough to be named after people. Well-known examples include ...

that allows for the preparation of carbonyls from primary or secondary

alkyl halides The haloalkanes (also known as halogenoalkanes or alkyl halides) are alkanes containing one or more halogen substituents. They are a subset of the general class of halocarbons, although the distinction is not often made. Haloalkanes are widely us ...

with the use of trialkylamine ''N''-oxides, such as ''N''-methylmorpholine ''N''-oxide or trimethylamine ''N''-oxide.

Mechanism

As in other

oxoammonium-catalyzed oxidation Oxoammonium-catalyzed oxidation reactions involve the conversion of organic substrates to more highly oxidized materials through the action of an N-oxoammonium species. Nitroxides may also be used in catalytic amounts in the presence of a stoichi ...

reactions, the negatively charged oxygen atom of the trialkylamine ''N''-oxide molecule attacks the alkyl halide in a S_N2 manner, kicking of the halide as a leaving group. A trialkylamine deprotonates the α-carbon atom, the resulting electron pair shifts onto the oxygen atom, which shifts its own excess electron pair onto the nitrogen atom. This generates the desired carbonyl, as well as the aforementioned trialkylamine. The reaction is an enhancement of the

Kornblum oxidation The Kornblum oxidation, named after Nathan Kornblum, is an organic oxidation reaction that converts alkyl halides and tosylates into carbonyl compounds. Mechanism Similar to sulfonium-based oxidation of alcohols to aldehydes reactions, the ...

protocol, which was originally developed using dimethyl sulfoxide or pyridine-''N''-oxide as the nucleophile.

Applications

The Ganem oxidation has been used as an intermediate step in the total synthesis of (−)-okilactomycin, converting a primary alkyl halide into an

aldehyde In organic chemistry, an aldehyde () is an organic compound containing a functional group with the structure . The functional group itself (without the "R" side chain) can be referred to as an aldehyde but can also be classified as a formyl grou ...

References

Name reactions {{chemistry-stub