Corey-Kim oxidation
The Corey-Kim oxidation is a chemical reaction used to synthesize aldehydes and ketones from primary and secondary alcohols. This reaction is named after the American chemist and Nobel Laureate Elias James Corey and Korean-American chemist Choung Un Kim[1].
The reagents involved in the Corey-Kim oxidation include N-chlorosuccinimide (NCS), dimethyl sulfide (DMS), and an organic base such as triethylamine (TEA). The reaction proceeds through the formation of a sulfonium salt when DMS reacts with NCS. This sulfonium salt is then attacked by the nucleophilic alcohol to form an alkoxysulfonium salt. Finally, the alkoxysulfonium salt is deprotonated by the base (TEA) to yield the corresponding carbonyl compound, either an aldehyde or a ketone, depending on whether the starting alcohol is primary or secondary[1][4][8][9][12].
The Corey-Kim oxidation is advantageous due to its mild reaction conditions and tolerance of many functional groups. However, it is less suitable for oxidizing allylic and benzylic alcohols, as these tend to be converted to the corresponding halides under Corey-Kim conditions[1][12]. To avoid the unpleasant odor associated with DMS, alternatives like dodecyl methyl sulfide have been used[1][2].
In terms of green chemistry, the Corey-Kim oxidation produces by-products such as DMSO, succinimide, and HCl. Efforts have been made to develop 'greener' options for this type of oxidation, focusing on the use of reagents that mitigate odor issues and facilitate work-up, although these alternatives can add to the process mass intensity (PMI) due to their multi-stage synthesis and energy requirements[2].
Overall, the Corey-Kim oxidation is a valuable tool in organic synthesis, often used with complex, multi-functional natural products, and has been subject to various improvements to address environmental and practical concerns[2][3][6].
Citations:
[1] https://en.wikipedia.org/wiki/Corey%E2%80%93Kim_oxidation
[2] https://reagents.acsgcipr.org/reagent-guides/oxidation-to-aldehyde-and-ketones/list-of-reagents/me2s-ncs-corey-kim-oxidation
[3] https://www.researchgate.net/publication/295687664_Application_of_Corey-Bakshi-Shibata_Corey-Kim_Corey-Seebach_Corey-Winter_Corey-Link_and_Corey-Ganem-Gilman_in_organic_and_total_synthesis
[4] https://www.jk-sci.com/blogs/resource-center/corey-kim-oxidation
[5] https://onlinelibrary.wiley.com/doi/10.1002/9780470638859.conrr159
[6] https://www.scribd.com/presentation/523001540/COREY-KIM
[7] https://www.sciencedirect.com/topics/chemistry/corey-kim-oxidation
[8] https://www.jkchemical.com/post/358
[9] https://www.name-reaction.com/corey-kim-oxidation
[10] https://www.youtube.com/watch?v=gV9DJ-nGG7I
[11] https://www.youtube.com/watch?v=fYgAUpDuJfY
[12] https://nrochemistry.com/corey-kim-oxidation/