Highly efficient heterogeneous polymer-supported Sharpless alkene epoxidation catalysts

Tetrahedron Asymmetry

Volumn 9, Issue 9, 1998, Pages 1563-1575

  Karjalainen, J K ^a   Hormi, O E O ^a   Sherrington, D C ^b  

^a UNIVERSITY OF OULU   (Finland)

^b UNIVERSITY OF STRATHCLYDE   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

EPOXIDE; TARTARIC ACID; TERT BUTYL HYDROPEROXIDE;

ARTICLE; CATALYST; CROSS LINKING; ENANTIOMER; EPOXIDATION; PRIORITY JOURNAL; STEREOCHEMISTRY;

EID: 0032496193     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0957-4166(98)00137-2     Document Type: Article

References (42)

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24. 1H NMR spectra.
25. The Sharpless catalytic method for asymmetric epoxidation was followed with slight modifications. Gao, Y.; Hanson, R. M.; Klunder, J. M.; Ko, S. Y.; Masamune, H.; Sharpless, K. B. J. Am. Chem. Soc. 1987, 109, 5765-5780.
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32. 25=+9 (c 1.6, THF). Optical rotation did not depend on the degree of branching/crosslinking. Some polymer batches were not soluble in hot THF and thus it was assumed that these polymers had degrees of branching/crosslinking ≫15% i.e. very much higher than THF soluble polymers (3-15%).
33. 1H NMR spectrum of poly(tartrate ester) 4: δ 5.41 (d, intensity=0.185H) +4.61 (d, 0.164H) [-OOC-CH(OCO-)-CH(OH)COO-, -OOC-CH(OCO-)-CH(OH)COO-, Scheme 1, unit y]/ 4.37 (s, 2.001H) [-OOC-CH(OH)-CH(OH)-COO-, Scheme 1, unit x]+y*100%=14.8%.
34. Development of a reusable heterogeneous epoxidation catalyst is under investigation in our laboratory.
35. nd Ed., Oxford University Press, 1990; pp. 360-368 and references therein.
36. Augustine, R. L. Heterogeneous Catalysis for the Synthetic Chemist; Marcel Dekker, Inc., New York, 1996; pp. 153-160.
37. The reaction rate was slower and enantioselectivity was not any better than at -20°C.
38. See Ref. 20. The metal alkoxide and metal alkyl catalysts are generally much more reactive in the presence of water or alcohols both of which are formed during the epoxidation reaction.
39. Enantioselectivity of geraniol oxide was 91% using L-(+)-diethyl tartrate as a ligand. See Ref. 12.
40. 2 and a sample was taken from a known volume for AAS-analysis.
41. An existing catalyzed process is improved by addition of a specific ligand, which leads to a faster, ligand-accelerated reaction. Both homogeneous and heterogeneous catalysts are known to exhibit this behavior. Berrisford, D. J.; Bolm, C.; Sharpless, K. B. Angew. Chem. Int. Ed. Engl. 1995, 34, 1059-1070.
42. Hill, J. G.; Rossiter, B. E.; Sharpless, K. B. J. Org. Chem. 1983, 48, 3607-3608.