The fluorous Swern and Corey-Kim reaction: scope and mechanism
David Crich* and Santosh Neelamkavil
*Departement of Chemistry, University of Illinois at Chicago, 845 West
Taylor Street, Chicago, IL 60607-7061, USA, Email: dcrich
uic.edu
D. Crich, S. Neelamkavil, Tetrahedron, 2002, 58, 3865-3870.
DOI: 10.1016/S0040-4020(02)00207-7
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Abstract
Fluorous sulfides and sulfoxides are effective odor-free reagents for the Corey-Kim and Swern oxidations of diversely functionalized primary and secondary alcohols to aldehydes and ketones. The reagents can be recovered in high yield by a continuous fluorous extraction of the reaction mixture.
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Details
The document discusses the development and application of fluorous Swern and Corey-Kim reactions for the oxidation of primary and secondary alcohols to aldehydes and ketones. Researchers David Crich and Santhosh Neelamkavil from the University of Illinois at Chicago report efficient protocols for preparing fluorous dimethyl sulfide and its oxidation to fluorous dimethyl sulfoxide. The fluorous Swern reaction, using fluorous dimethyl sulfoxide with oxalyl chloride and Hunig's base, achieves high yields and allows for the recovery and reuse of the fluorous reagent through a simple extraction and reoxidation process. This method is environmentally friendly, odor-free, and retains the mild conditions and broad applicability of the classical Swern reaction. The mechanism involves intramolecular hydride abstraction from a sulfur ylid. Additionally, a fluorous version of the Corey-Kim reaction is explored, though it requires near-stoichiometric amounts of the fluorous sulfide for high recovery rates. The study emphasizes the importance of fluorous chemistry in developing cleaner, more efficient, and recyclable chemical processes.
Key Words
Oxidation, Ylids, Sulfoxides, Fluorine and Compounds, Swern Oxidation, Corey-Kim Oxidation, Aldehydes, Ketones
ID: J72-Y2002-100
