期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 25, 期 63, 页码 14460-14468出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201903752
关键词
anomeric effects; carbonyl compounds; peroxides; peroxycarbenium ion; stereoelectronic effects
资金
- Russian Science Foundation [19-73-20190]
- Ministry of Science and Higher Education of the Russian Federation
- Russian Science Foundation [19-73-20190] Funding Source: Russian Science Foundation
Stereoelectronic interactions control reactivity of peroxycarbenium cations, the key intermediates in (per)oxidation chemistry. Computational analysis suggests that alcohol involvement as a third component in the carbonyl/peroxide reactions remained invisible due to the absence of sufficiently deep kinetic traps needed to prevent the escape of mixed alcohol/peroxide products to the more stable bisperoxides. Synthesis of beta-alkoxy-beta-peroxylactones, a new type of organic peroxides, was accomplished by interrupting a thermodynamically driven peroxidation cascade. The higher energy beta-alkoxy-beta-peroxylactones do not transform into the more stable bisperoxides due to the stereoelectronically imposed instability of a cyclic peroxycarbenium intermediate as a consequence of amplified inverse alpha-effect. The practical consequence of this fundamental finding is the first three-component cyclization/condensation of beta-ketoesters, H2O2, and alcohols that provides beta-alkoxy-beta-peroxylactones in 15-80 % yields.
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