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- Title
The oxidation of secondary alcohols by dimethyldioxirane: re-examination of kinetic isotope effects.
- Authors
Baumstark, Alfons L.; Vasquez, Pedro C.; Cunningham, Mark; Leggett-Robinson, Pamela M.
- Abstract
The kinetic isotope effects for the oxidation of a series of deuterated isopropanols and α-trideuteromethyl benzyl alcohol by dimethyldioxirane (1) to the corresponding ketones were determined in dried acetone at 23°C. A primary kinetic isotope effect (PKIE) of 5.2 for the oxidation of isopropyl-2-d alcohol by 1 was obtained. The SKIEs for oxidation of α-trideuteromethyl benzyl alcohol and isopropyl-1,1,1,3,3,3-d6 alcohol were found to be 1.07 and 0.98, respectively. Oxidation of isopropanol-d by 1 yielded a kOH/kOD value of 1.12, which is similar to that previously reported for α-methylbenzyl alcohol-d. Both normal and inverse secondary kinetic isotope effect (SKIEs) are observed. Mechanistically, the results indicate that the process is more complex than the previously proposed models.
- Publication
Heterocyclic Communications, 2010, Vol 16, Issue 4-6, p217
- ISSN
0793-0283
- Publication type
Article
- DOI
10.1515/HC.2010.016