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Interrupted Baeyer–Villiger Rearrangement: Building A Stereoelectronic Trap for the Criegee Intermediate |
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| Authors: | Dr Vera A Vil' Gabriel dos?Passos?Gomes Oleg V Bityukov Prof Konstantin A Lyssenko Prof Gennady I Nikishin Prof Igor V Alabugin Prof Alexander O Terent'ev |
| Institution: | 1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russian Federation;2. D. I. Mendeleev University of Chemical Technology of Russia, Moscow, Russian Federation;3. All-Russian Research Institute for Phytopathology, Moscow Region, Russian Federation;4. Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL, USA;5. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russian Federation |
| Abstract: | The instability of hydroxy peroxyesters, the elusive Criegee intermediates of the Baeyer–Villiger rearrangement, can be alleviated by selective deactivation of the stereoelectronic effects that promote the 1,2‐alkyl shift. Stable cyclic Criegee intermediates constrained within a five‐membered ring can be prepared by mild reduction of the respective hydroperoxy peroxyesters (β‐hydroperoxy‐β‐peroxylactones) which were formed in high yields in reaction of β‐ketoesters with BF3?Et2O/H2O2. |
| Keywords: | anomeric effects Baeyer– Villiger reaction peroxides reactive intermediates stereoelectronics |