View source for Chemistry:Corey–Kim oxidation

{{Reactionbox
| Name = Corey-Kim oxidation
| Type = Organic redox reaction
| NamedAfter = [[Biography:Elias James Corey|Elias James Corey]] <br/> Choung Un Kim
| Section3 = {{Reactionbox Identifiers
   | OrganicChemistryNamed = corey-kim-oxidation
 }}
}}
The '''Corey&ndash;Kim oxidation''' is an 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
|author1=E. J. Corey |author2=C. U. Kim | journal =  [[Organization:Journal of the American Chemical Society|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
|author1=E. J. Corey |author2=C. U. Kim | journal =  [[Chemistry:Tetrahedron Letters|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&ndash;Kim Reagent
|author1=S. Katayama |author2=K. Fukuda |author3=T. Watanabe |author4=M. Yamauchi | journal =  Synthesis
| year = 1988
| volume = 1988| issue = 3
| 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 =  1990| issue = 10
| 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
|author1=J. T. Pulkkinen |author2=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 Nobel Laureate [[Biography:Elias James Corey|Elias James Corey]] and Korean-American chemist Choung Un Kim.

[[Image:Corey-Kim Oxidation Scheme.png|center|350px|The Corey&ndash;Kim oxidation]]

Although the Corey&ndash;Kim oxidation possesses the distinctive advantage over [[Chemistry:Swern oxidation|Swern oxidation]] of allowing an operation above –25&nbsp;°C, it is not so commonly used due to issues with selectivity in substrates susceptible to chlorination by [[Chemistry:N-Chlorosuccinimide|''N''-chlorosuccinimide]].

==Reaction mechanism==

[[Chemistry:Dimethyl sulfide|Dimethyl sulfide]] (Me<sub>2</sub>S) is treated with [[Chemistry:N-Chlorosuccinimide|''N''-chlorosuccinimide]] (NCS), resulting in formation of an "active DMSO" species that is used for the activation of the alcohol. Addition of [[Chemistry:Triethylamine|triethylamine]] 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).

[[File:Corey-Kim oxidation mechanism.svg|center|680px|The reaction mechanism of Corey–Kim oxidation]]

Under Corey&ndash;Kim conditions allylic and benzylic [[Chemistry:Alcohol|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 [[Chemistry:Triethylamine|triethylamine]]. In fact, Corey&ndash;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 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'' '''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'' '''2002''', ''58'', 3865–3870.</ref> utilized fluorous technology in a similar manner.

==See also==
*[[Chemistry:Pfitzner–Moffatt oxidation|Pfitzner–Moffatt oxidation]]
*[[Chemistry:Sulfonium-based oxidation of alcohols to aldehydes|Sulfonium-based oxidation of alcohols to aldehydes]]

==References==
{{Reflist}}

==External links==
*[https://www.organic-chemistry.org/namedreactions/corey-kim-oxidation.shtm Corey&ndash;Kim Oxidation from Organic-Chemistry]
{{Organic reactions}}
{{DEFAULTSORT:Corey-Kim oxidation}}
[[Category:Organic oxidation reactions]]
[[Category:Name reactions]]

{{Sourceattribution|Corey–Kim oxidation}}