Ganem Oxidation

The Ganem oxidation is a name reaction in organic chemistry that allows for the preparation of carbonyls from primary or secondary alkyl halides. The reaction uses trialkylamine N-oxides, such as N-methylmorpholine N-oxide or trimethylamine N-oxide, as the oxidizing agent. The mechanism involves the negatively charged oxygen atom of the trialkylamine N-oxide molecule attacking the alkyl halide, which results in the halide leaving the molecule. A trialkylamine then deprotonates the α-carbon atom, and 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[2].

The Ganem oxidation is an enhancement of the Kornblum oxidation protocol, which was originally developed using dimethyl sulfoxide or pyridine-N-oxide as the nucleophile[2][4]. The Ganem oxidation has been used as an intermediate step in the total synthesis of (−)-okilactomycin, converting a primary alkyl halide into an aldehyde[2].

Citations:

[1] https://academic-accelerator.com/encyclopedia/ganem-oxidation

[2] https://en.wikipedia.org/wiki/Ganem_oxidation

[3] https://onlinelibrary.wiley.com/doi/10.1002/anie.202214096

[4] https://en.wikipedia.org/wiki/Kornblum_oxidation

[5] https://nrochemistry.com/corey-gilman-ganem-oxidation/

[6] https://pubs.acs.org/doi/10.1021/ja01022a059

[7] https://www.chemeurope.com/en/encyclopedia/Kornblum_oxidation.html

[8] https://en.chem-station.com/reactions-2/2014/01/corey-gilman-ganem-oxidation.html

[9] https://www.sciencedirect.com/science/article/abs/pii/S004040390102161X

[10] https://academic-accelerator.com/encyclopedia/kornblum-oxidation

[11] https://www.youtube.com/watch?v=5gPhh6m52VI

[12] https://organicchemistrydata.org/hansreich/resources/redox/?page=redox23%2F

[13] https://www.youtube.com/watch?v=307TtyOYqrI

[14] https://synarchive.com/named-reactions/ganem-oxidation

[15] https://link.springer.com/referenceworkentry/10.1007/978-0-387-48998-8_1173

[16] https://chem.libretexts.org/Courses/University_of_California_Davis/Chem_231A%3A_Methods_of_Organic_Synthesis/Text/Oxidations/Oxidation_of_Aldehydes

[17] https://en.wikipedia.org/wiki/List_of_organic_reactions

[18] https://www.wikiwand.com/en/Ganem_oxidation

[19] https://www.yumpu.com/en/document/view/8942123/module-i-oxidation-reactions-nptel