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Electron Transfer‐Initiated Epoxidation and Isomerization Chain Reactions of β‐Caryophyllene
Authors:Bart Steenackers  Nicolò Campagnol  Prof Jan Fransaer  Prof Ive Hermans  Prof Dirk De?Vos
Institution:1. Centre for Surface Chemistry and Catalysis, KU Leuven, Kasteelpark Arenberg?23, 3001 Leuven (Belgium), Fax: (+32)?6321998;2. Department of Materials Engineering, KU Leuven, Kasteelpark Arenberg 23, 3001 Leuven (Belgium);3. Department of Chemistry & Department of Chemical and Biological Engineering, The University of Wisconsin‐Madison, 1101 University Avenue, 53706 Madison WI (USA)
Abstract:The abundant sesquiterpene β‐caryophyllene can be epoxidized by molecular oxygen in the absence of any catalyst. In polar aprotic solvents, the reaction proceeds smoothly with epoxide selectivities exceeding 70 %. A mechanistic study has been performed and the possible involvement of free radical, spin inversion, and electron transfer mechanisms is evaluated using experimental and computational methods. The experimental data—including a detailed reaction product analysis, studies on reaction parameters, solvent effects, additives and an electrochemical investigation—all support that the spontaneous epoxidation of β‐caryophyllene constitutes a rare case of unsensitized electron transfer from an olefin to triplet oxygen under mild conditions (80 °C, 1 bar O2). As initiation of the oxygenation reaction, the formation of a caryophyllene‐derived radical cation via electron transfer is proposed. This radical cation reacts with triplet oxygen to a dioxetane via a chain mechanism with chain lengths exceeding 100 under optimized conditions. The dioxetane then acts as an in situ‐formed epoxidizing agent. Under nitrogen atmosphere, the presence of a one‐electron acceptor leads to the selective isomerization of β‐caryophyllene to isocaryophyllene. Observations indicate that this isomerization reaction is a novel and elegant synthetic pathway to isocaryophyllene.
Keywords:epoxidation  isomerization  radical ions  reaction mechanisms  sesquiterpenes
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