Iron-Catalyzed Asymmetric Sulfide Oxidation with Aqueous Hydrogen Peroxide

Angewandte Chemie - International Edition

Volumn 42, Issue 44, 2003, Pages 5487-5489

  Legros, Julien ^a   Bolm, Carsten ^a  

^a RWTH AACHEN UNIVERSITY   (Germany)

Author keywords

Asymmetric catalysis; Iron; Oxidation; Peroxides; Sulfoxides

Indexed keywords

CATALYST ACTIVITY; HYDROGEN PEROXIDE; OXIDATION;

OXIDANTS;

SULFUR COMPOUNDS;

HYDROGEN PEROXIDE; IRON;

AQUEOUS SOLUTION; ARTICLE; ASYMMETRIC SYNTHESIS; BIOAVAILABILITY; BIOTRANSFORMATION; ECONOMICS; ENANTIOSELECTIVITY; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; OXIDATION; PHASE TRANSITION; ULTRAVIOLET SPECTROSCOPY;

EID: 0344845085     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200352635     Document Type: Article

References (32)

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4. For a recent comparative assessment of asymmetric oxidations, see: C. Bonini, G. Righi, Tetrahedron 2002, 58, 4981-5021.
5. Efficient asymmetric sulfide oxidations are required in various processes towards pharmaceutically relevant molecules. One of the most important is the synthesis of the chiral sulfoxide, omeprazole, which is one of the most sold drugs in the world (sales in 2002: US$6.6 billion). For a summary of recent developments and data, see: A. M. Rouhi, Chem. Eng. News 2003, 81(19), 56-61.
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12. Recently, niobium and tungsten complexes have also been involved in asymmetric sulfoxidation reactions: a) Nb: T. Miyazaki, T. Katsuki, Synlett 2003, 1046-1048;
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22. Such ligands have also been used in vanadium-catalyzed asymmetric sulfide oxidations; see: a) C. Bolm, F. Bienewald, Angew. Chem. 1995, 107, 2883-2885; Angew. Chem. Int. Ed. Engl. 1995, 34, 2640-2642;
23. Such ligands have also been used in vanadium-catalyzed asymmetric sulfide oxidations; see: a) C. Bolm, F. Bienewald, Angew. Chem. 1995, 107, 2883-2885; Angew. Chem. Int. Ed. Engl. 1995, 34, 2640-2642;
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30. 2 adduct (UHP) also gives satisfactory results.
31. 2, complete conversion of sulfide into racemic sulfoxide and sulfone was observed. In independent experiments, it was demonstrated that the sulfoxide to sulfone oxidation proceeded in a non-enantioselective manner.
32. Attempts to substitute dichloromethane with other solvents such as acetonitrile, acetone, toluene, or tert-butyl methyl ether were unsuccessful.