Institution: | 1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prospect, Moscow, 119991 Russian Federation;2. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prospect, Moscow, 119991 Russian Federation
All-Russian Research Institute for Phytopathology, B. Vyazyomy, Moscow Region, 143050 Russian Federation;3. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Street, Moscow, 119991 Russian Federation
Pirogov Russian National Research Medical University, Moscow, 117997 Russian Federation;4. Department of Chemistry and Biochemistry, Florida State University, Tallahassee, 32309 USA |
Abstract: | 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 β-alkoxy-β-peroxylactones, a new type of organic peroxides, was accomplished by interrupting a thermodynamically driven peroxidation cascade. The higher energy β-alkoxy-β-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 β-ketoesters, H2O2, and alcohols that provides β-alkoxy-β-peroxylactones in 15–80 % yields. |