Corey-Kim oxidation

The Corey-Kim oxidation is an oxidation reaction used to synthesise aldehydes and ketones from primary and secondary alcohols. [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] [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] [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] [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] [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] It is named for American chemist and Nobelist Elias James Corey and Korean-American chemist Choung Un Kim.

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

Dimethyl sulfide (Me₂S) 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 alcohols 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." [Ohsugia, S.-I.; Nishidea, K.; Oonob, K.; Okuyamab, K.; Fudesakaa, M.; Kodamaa, S.; Node, M. "Tetrahedron" 2003, "59", 8393-8398.] substituted a long-chain sulfide, dodecyl methyl sulfide, for dimethyl sulfide. Crich "et al." [Crich, D.; Neelamkavil, S. "Tetrahedron" 2002, "58", 3865-3870.] utilized fluorous technology in a likewise manner.

References

ee also

*Pfitzner-Moffatt oxidation

External links

* [http://www.organic-chemistry.org/namedreactions/corey-kim-oxidation.shtm Corey-Kim Oxidation from Organic-Chemistry]