Biomimetic High-Valent Non-Heme Iron Oxidants for the cis-Dihydroxylation and Epoxidation of Olefins

Biomimetic High-Valent Non-Heme Iron Oxidants for the cis-Dihydroxylation and Epoxidation of Olefins

Pathfinding: The iron(II) complex of the bispidine ligand L1 is oxidized with H2O2 to intermediate‐spin [(L1)FeIV(OH)2]2+ (1, see picture) which forms cis diols 2 from olefins, and the high‐spin [(L1)FeIVO(OH2)]2+ ferryl complex (3) results in epoxidation (4). Product distributions (diol/epoxide) a...

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Veröffentlicht in:Angewandte Chemie (International ed.) 2007-01, Vol.46 (42), p.8067-8070
Hauptverfasser: Bautz, Jochen, Comba, Peter, Lopez de Laorden, Carlos, Menzel, Matthias, Rajaraman, Gopalan
Format: Artikel
Sprache:eng
Schlagworte:
Alkenes - chemistry
Biomimetics
Bridged Bicyclo Compounds, Heterocyclic - chemistry
dihydroxylation
epoxidation
Ferric Compounds - chemical synthesis
Ferric Compounds - chemistry
Ferrous Compounds - chemical synthesis
Ferrous Compounds - chemistry
Hydrogen Peroxide - chemistry
Hydroxylation
iron
Ligands
Models, Chemical
Molecular Structure
Organometallic Compounds - chemical synthesis
Organometallic Compounds - chemistry
Oxidants - chemical synthesis
Oxidants - chemistry
oxidation
Oxidation-Reduction
reaction mechanisms
Stereoisomerism
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Beschreibung
Zusammenfassung:Pathfinding: The iron(II) complex of the bispidine ligand L1 is oxidized with H2O2 to intermediate‐spin [(L1)FeIV(OH)2]2+ (1, see picture) which forms cis diols 2 from olefins, and the high‐spin [(L1)FeIVO(OH2)]2+ ferryl complex (3) results in epoxidation (4). Product distributions (diol/epoxide) and 18O labeling studies are used to propose a mechanism, which is fully supported by DFT analyses.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.200701681