Lemieux-Johnson Oxidation
The Lemieux–Johnson oxidation, also known as the Malaprade–Lemieux–Johnson oxidation, is a chemical reaction used to cleave carbon-carbon double bonds in olefins, converting them into aldehydes or ketones. This reaction is named after Raymond Urgel Lemieux and William Summer Johnson, who published the method in 1956[1].
The reaction proceeds in two steps:
- Dihydroxylation of the alkene using osmium tetroxide (OsO4), which adds two hydroxyl groups across the double bond to form a vicinal diol.
- Oxidative cleavage of the diol by a periodate (such as sodium periodate, NaIO4), in a process known as the Malaprade reaction, to yield the carbonyl compounds.
A key feature of the Lemieux–Johnson oxidation is that it can stop at the aldehyde stage without further oxidation to carboxylic acids. This is in contrast to other oxidative cleavage reactions, such as ozonolysis or potassium permanganate (KMnO_4) treatment, which may over-oxidize the aldehyde to a carboxylic acid[1][4].
The classical Lemieux–Johnson oxidation can sometimes result in low yields due to the formation of side products. However, the addition of non-nucleophilic bases like 2,6-lutidine can improve the reaction's efficiency. Additionally, OsO4 can be used in catalytic amounts because excess periodate in the reaction mixture can regenerate the consumed OsO4[1][4].
Variations of the reagent and conditions have been developed to optimize the reaction for different substrates. For example, osmium compounds other than OsO4 and oxidizing agents other than periodate can be used. The reaction has been employed in the cleavage of the carbon-carbon double bond of shikimic acid derivatives and other complex molecules[2][7].
The Lemieux–Johnson oxidation is a valuable tool in organic synthesis, particularly when selective cleavage of double bonds is desired without over-oxidation to carboxylic acids.
Citations:
[1] https://en.wikipedia.org/wiki/Lemieux%E2%80%93Johnson_oxidation
[2] https://www.researchgate.net/publication/340737639_Lemieux-Johnson_reagent
[3] https://pubs.acs.org/doi/10.1021/acs.oprd.2c00161
[4] https://synarchive.com/named-reactions/lemieux-johnson-oxidation
[5] https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202213772
[6] https://onlinelibrary.wiley.com/doi/10.1002/9780470638859.conrr389
[7] https://www.researchgate.net/publication/312922794_A_Lemieux-Johnson_oxidation_of_shikimic_acid_derivatives_facile_entry_to_small_library_of_protected_2S3S4R-2347-tetrahydroxy-6-oxoheptanals
[8] https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2848477/
[9] https://youtube.com/watch?v=YDXefSKdVlk
[10] https://www.chemistrysteps.com/naio4-alcohol-reaction-mechanism/
[11] https://www.sciencedirect.com/topics/chemistry/lemieux-von-rudloff-reaction
[12] https://youtube.com/watch?v=_InFs9SiDTs