Corey-Kim Oxidation

N-chlorosuccinimide (NCS), dimethylsulfide (DMS) and triethylamine (TEA) are used to efficiently convert 1° or 2° alcohols into aldehydes and ketones respectively. First, NCS and DMS react to form the Corey-Kim reagent or S,S-dimethylsuccinimidosulfonium chloride, via dimethylsulfonium chloride. The nucleophilic 1° or 2° alcohol then attacks the Corey-Kim reagent, resulting in an alkoxysulfonium salt, which is deprotonated by TEA to form the desired carbonyl compound. Regenerated DMS is readily removed from the reaction mixture in vacuo.

Lab Tips:

Dodecylmethylsulfide can be used instead of DMS for an odorless Corey-Kim oxidation. ^[1]
Most functional and protecting groups are tolerated with the Corey-Kim reaction conditions. ^[2]
Allylic and benzylic alcohols are not oxidized because they are predominantly converted to allylic and benzylic halides. ^[2]
A side-reaction may occur in polar solvents in which the alcohol forms the corresponding methylthiomethyl ether (ROCH₂SCH₃). ^[2]
The Corey-Kim reagent can also be used to dehydrate aldoximes to nitriles, ^[3] convert 3-hydroxycarbonyl compounds to 1,3-dicarbonyls, ^[4] synthesize stable sulfur ylides from active methylene compounds, ^[5] and to prepare 3(H)-indoles from 1(H)-indoles. ^[6]

_{1. Nishide, K., Ohsugi, S.-i., Fudesaka, M., Kodama, S., Node, M. New odorless protocols for the Swern and Corey-Kim oxidations. Tetrahedron Lett. 2002, 43, 5177-5179.
2. Kürti, L., Czakó, B. (2005). Strategic Applications of Named Reactions in Organic Synthesis; Background and Detailed Mechanisms. Burlington, MA: Elsevier Academic Press.
3. Ho, T.-L., Wong, C. M. Nitrile synthesis. Use of Corey-Kim system as dehydrant of aldoximes. Synth. Commun. 1975, 5, 423-425.
4. Katayama, S., Fukuda, K., Watanabe, T., Yamauchi, M. Synthesis of 1,3-dicarbnyl compounds by the oxidation of 3-hydroxycarbonyl compounds with Corey-Kim reagent. Synthesis 1988, 178-183.
5. Katayama, S., Watanabe, T., Yamauchi, M. Convenient synthesis of stable sulfur ylides by reaction of active methylene compounds with Corey-Kim reagent. Chem. Pharm. Bull. 1990, 38, 3314-3316.
6. Katayama, S., Watanabe, T., Yamauchi, M. Convenient synthesis of 3H-indoles (indolenines) by reaction of 1H-indoles with Corey-Kim reagent. Chem. Pharm. Bull. 1992, 40, 2836-2838.}