Journal
KINETICS AND CATALYSIS
Volume 54, Issue 5, Pages 607-614Publisher
MAIK NAUKA/INTERPERIODICA/SPRINGER
DOI: 10.1134/S0023158413050169
Keywords
allylic oxidation; alkenes; terpenes; molecular oxygen; porous coordination polymers; MIL-101
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Funding
- Russian Foundation for Basic Research [09-03-93109, 13-03-00314]
- CNRS
- French Embassy in Moscow
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The catalytic performances of Cr-MIL-101 and Fe-MIL-101 porous coordination polymers have been investigated in the allylic oxidation of alkenes, including natural terpenes, with molecular oxygen (1 atm) under mild solvent-free conditions. Both catalysts remain stable under optimal conditions (40A degrees C for Fe-MIL-101 and 60A degrees C for Cr-MIL-101) and can be recycled, at least, four times without loss of the catalytic properties. Fe-MIL-101 favours the formation of unsaturated alcohols, while Cr-MIL-101 mediates the formation of unsaturated ketones. The oxidation process involves the formation of alkene hydroperoxide via conventional radical chain process and its further transformations over the MIL-101 catalysts. The mechanism of the hydroperoxide transformation strongly depends on the metal nature.
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