Corey-Kim oxidation
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The '''Corey-Kim oxidation''' is an [[organic oxidation|oxidation reaction]] used to synthesise [[aldehydes]] and [[ketones]] from primary and secondary [[alcohols]].<ref>{{cite journal
| title = New and highly effective method for the oxidation of primary and secondary alcohols to carbonyl compounds
| author = E. J. Corey, C. U. Kim
| journal = [[Journal of the American Chemical Society]]
| year = 1972
| volume = 94
| issue = 21
| pages = 7586–7587
| doi = 10.1021/ja00776a056
}}</ref><ref>{{cite journal
| title = A method for the oxidation of sec,tert -1,2-diols to α-hydroxy ketones without carbon-carbon cleavage
| author = E. J. Corey, C. U. Kim
| journal = [[Tetrahedron Letters]]
| year = 1974
| volume = 15
| issue = 3
| pages = 287–290
| doi = 10.1016/S0040-4039(01)82195-X
}}</ref><ref>{{cite journal
| title = Synthesis of 1,3-Dicarbonyl Compounds by the Oxidation of 3-Hydroxycarbonyl Compounds with Corey-Kim Reagent
| author = S. Katayama, K. Fukuda, T. Watanabe, M. Yamauchi
| journal = [[Synthesis]]
| year = 1988
| volume =
| issue =
| pages = 178–183
| doi = 10.1055/s-1988-27506
}}</ref><ref>{{cite journal
| title = Oxidation of Alcohols by Activated Dimethyl Sulfoxide and Related Reactions: An Update
| author = T. T. Tidwell
| journal = [[Synthesis]]
| year = 1990
| volume =
| issue =
| pages = 857–870
| doi = 10.1055/s-1990-27036
}}</ref><ref>{{cite journal
| title = 3-Unsubstituted 1,5-Diaryl-2,4-pentanediones and -4-methoxy-2-pentanones: Synthesis via Corresponding 3-Hydroxy Ketones Generated from 2-Isoxazolines
| author = J. T. Pulkkinen, J. J. Vepsäläinen
| journal = [[Journal of Organic Chemistry]]
| year = 1996
| volume = 61
| issue = 24
| pages = 8604–8609
| doi = 10.1021/jo960887a
}}
</ref> It is named for American chemist and Nobelist [[Elias James Corey]] and Korean-American chemist [[Choung Un Kim]].
[[Image:Corey-Kim Oxidation Scheme.png|center|350px|The Corey-Kim oxidation]]
Although the Corey-Kim oxidation possesses the distinctive advantage over [[Swern oxidation]] of allowing an operation above –25 ºC, it is not so commonly used because of the need to employ [[dimethyl sulfide]], a poisonous and volatile liquid with a very bad odor.
==Reaction mechanism==
[[Image:CKoxidation.gif|center|The mechanism of the Corey-Kim oxidation]]
[[Dimethyl sulfide]] (Me<sub>2</sub>S) is treated with ''N''-chlorosuccinimide (NCS), resulting in formation of an "active DMSO" species that is used for the activation of the alcohol. Addition of [[trimethylamine]] to the activated alcohol leads to its oxidation to aldehyde or ketone and generation of dimethyl sulfide. In variance with other alcohol oxidation using "activated DMSO," the reactive oxidizing species is not generated by reaction of DMSO with an electrophile. Rather, it is formed by oxidation of dimethyl sulfide with an oxidant (NCS).
Under Corey-Kim conditions [[allylic]] and [[benzylic]] [[alcohol]]s have a tendency to evolve to the corresponding allyl and benzyl chlorides unless the alcohol activation is very quickly followed by addition of [[triethylamine]]. In fact, Corey-Kim conditions —with no addition of triethylamine— are very efficient for the transformation of allylic and benzylic alcohols to chlorides in presence of other alcohols.
==Variations==
Substituting dimethyl sulfide with a something less noxious has been the goal of several research projects. Ohsugia ''et al.''<ref>Ohsugia, S.-I.; Nishidea, K.; Oonob, K.; Okuyamab, K.; Fudesakaa, M.; Kodamaa, S.; Node, M. ''[[Tetrahedron (journal)|Tetrahedron]]'' '''2003''', ''59'', 8393-8398.</ref> substituted a long-chain sulfide, dodecyl methyl sulfide, for dimethyl sulfide. Crich ''et al.''<ref>Crich, D.; Neelamkavil, S. ''[[Tetrahedron (journal)|Tetrahedron]]'' '''2002''', ''58'', 3865-3870.</ref> utilized fluorous technology in a likewise manner.
==References==
{{Reflist}}
==See also==
*[[Pfitzner-Moffatt oxidation]]
==External links==
*[http://www.organic-chemistry.org/namedreactions/corey-kim-oxidation.shtm Corey-Kim Oxidation from Organic-Chemistry]
[[Category:Organic redox reactions]]
[[Category:Name reactions]]