Criegee oxidation
| Criegee oxidation | |
|---|---|
| Named after | Rudolf Criegee |
| Reaction type | Organic redox reaction |
| Identifiers | |
| RSC ontology ID | RXNO:0000257 |
The Criegee oxidation is a glycol cleavage reaction in which vicinal diols are oxidized to form ketones and aldehydes using lead tetraacetate. It is analogous to the use of periodate (Malaprade reaction) but uses a milder oxidant. This oxidation was discovered by Rudolf Criegee and coworkers and first reported in 1931 using ethylene glycol as the substrate.[1]
The rate of the reaction is highly dependent on the relative geometric position of the two hydroxyl groups, so much so that diols that are cis on certain rings can be reacted selectively as opposed to those that are trans on them.[2] It was heavily stressed by Criegee that the reaction must be run in anhydrous solvents, as any water present would hydrolyze the lead tetraacetate; however, subsequent publications have reported that if the rate of oxidation is faster than the rate of hydrolysis, the cleavage can be run in wet solvents or even aqueous solutions.[3] For example, glucose, glycerol, mannitol, and xylose can all undergo a Criegee oxidation in aqueous solutions, but sucrose cannot.[4][5]
- ^ Criegee, R. (1931). "Eine oxydative Spaltung von Glykolen". Berichte der Deutschen Chemischen Gesellschaft. 64: 260–266. doi:10.1002/cber.19310640212.
- ^ Reeves, Richard E. (1949). "Direct Titration of cis-Glycols with Lead Tetraacetate". Analytical Chemistry. 21 (6): 751. doi:10.1021/ac60030a035.
- ^ Baer, Erich; Grosheintz, J. M.; Fischer, Hermann O. L. (1939). "Oxidation of 1,2-Glycols or 1,2,3-Polyalcohols by Means of Lead Tetraacetate in Aqueous Solution". Journal of the American Chemical Society. 61 (10): 2607–2609. doi:10.1021/ja01265a010.
- ^ Hockett, Robert C.; Zief, Morris (1950). "Lead Tetraacetate Oxidations in the Sugar Group. XI. The Oxidation of Sucrose and Preparation of Glycerol and Glycol". Journal of the American Chemical Society. 72: 2130–2132. doi:10.1021/ja01161a073.
- ^ Abraham, Samuel (1950). "The Quantitative Recovery of Carbon Dioxide in Lead Tetraacetate Oxidations of Sugars and Sugar Derivatives". Journal of the American Chemical Society. 72 (9): 4050–4053. doi:10.1021/ja01165a058.