An improved heterogeneous asymmetric epoxidation of homoallylic alcohols using polymer-supported Ti(IV) catalysts

Tetrahedron Asymmetry

Volumn 9, Issue 21, 1998, Pages 3895-3901

  Karjalainen, Jaana K ^a   Hormi, Osmo E O ^a   Sherrington, David C ^a  

^a UNIVERSITY OF OULU   (Finland)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYL ALCOHOL; POLYMER; TARTARIC ACID; TERT BUTYL HYDROPEROXIDE; TITANIUM;

ARTICLE; CATALYST; EPOXIDATION; PRIORITY JOURNAL; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0032491549     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0957-4166(98)00408-X     Document Type: Article

References (12)

1. Rossiter, B. E. Asymmetric Synthesis; Academic Press: Orlando, FL, 1985; Vol. 5, pp. 193-246.
2. Rossiter, B. E.; Sharpless, K. B. J. Org. Chem. 1984, 49, 3707-3711.
3. 4 which has a longer metal-oxygen bond than the Ti complex, the enantioselectivity in the epoxidation of cis-homoallylic alcohol is higher. Ikegami, S.; Katsuki, T.; Yamaguchi, M. Chem. Lett. 1987, 83-84.
4. (a) Canali, L.; Karjalainen, J. K.; Hormi, O.; Sherrington, D. C. J. Chem. Soc., Chem. Commun. 1997, 123-124
5. (b) Karjalainen, J. K.; Hormi, O. E. O.; Sherrington, D. C. Molecules 1998, 3, 51-59.
6. Karjalainen, J. K.; Hormi, O. E. O.; Sherrington, D. C. Tetrahedron: Asymmetry 1998, 9, 1563-1575.
7. Karjalainen, J. K.; Hormi, O. E. O.; Sherrington, D. C. Tetrahedron: Asymmetry 1998, 9, 2019-2022.
8. Raifel'd, Y. E.; Vaisman, A. M. Russ. Chem. Rev. 1991, 60, 123-145.
9. n, n=2, 6, 8, 12) revealed that intramolecular polymer-Ti complexes, where the tartaric units are adjacent in the chain, are feasible for 6, 8, 12. When n=2, such regular rigid structures are not possible due to the geometric constraints imposed by the short alkyl chain. Therefore, good enantioselectivity is expected only for the polymers with longer alkyl chains. The same feature was also observed according to the results shown in Ref. 4. In the light of these results we think that the complex between the polymer and titanium is intramolecular, (a) Turbomole 96.0/4.0.0 User Guide, September 1996, San Diego: Molecular Simulations, 1996. (b) Discover 96.0/4.0.0 User Guide, September 1996, San Diego: Molecular Simulations, 1996. The pcff force field used in the calculations was modified to fit the torsional behaviour of some model molecules at the MP2/6-31G(d) level of theory. Details of the modifications will be described elsewhere (Korpelainen, V.; Ahjopalo, L.; Mannfors, B.; Pietilä, L. O. in preparation).
10. n, n=2, 6, 8, 12) revealed that intramolecular polymer-Ti complexes, where the tartaric units are adjacent in the chain, are feasible for 6, 8, 12. When n=2, such regular rigid structures are not possible due to the geometric constraints imposed by the short alkyl chain. Therefore, good enantioselectivity is expected only for the polymers with longer alkyl chains. The same feature was also observed according to the results shown in Ref. 4. In the light of these results we think that the complex between the polymer and titanium is intramolecular, (a) Turbomole 96.0/4.0.0 User Guide, September 1996, San Diego: Molecular Simulations, 1996. (b) Discover 96.0/4.0.0 User Guide, September 1996, San Diego: Molecular Simulations, 1996. The pcff force field used in the calculations was modified to fit the torsional behaviour of some model molecules at the MP2/6-31G(d) level of theory. Details of the modifications will be described elsewhere (Korpelainen, V.; Ahjopalo, L.; Mannfors, B.; Pietilä, L. O. in preparation).
11. n, n=2, 6, 8, 12) revealed that intramolecular polymer-Ti complexes, where the tartaric units are adjacent in the chain, are feasible for 6, 8, 12. When n=2, such regular rigid structures are not possible due to the geometric constraints imposed by the short alkyl chain. Therefore, good enantioselectivity is expected only for the polymers with longer alkyl chains. The same feature was also observed according to the results shown in Ref. 4. In the light of these results we think that the complex between the polymer and titanium is intramolecular, (a) Turbomole 96.0/4.0.0 User Guide, September 1996, San Diego: Molecular Simulations, 1996. (b) Discover 96.0/4.0.0 User Guide, September 1996, San Diego: Molecular Simulations, 1996. The pcff force field used in the calculations was modified to fit the torsional behaviour of some model molecules at the MP2/6-31G(d) level of theory. Details of the modifications will be described elsewhere (Korpelainen, V.; Ahjopalo, L.; Mannfors, B.; Pietilä, L. O. in preparation).
12. n, n=2, 6, 8, 12) revealed that intramolecular polymer-Ti complexes, where the tartaric units are adjacent in the chain, are feasible for 6, 8, 12. When n=2, such regular rigid structures are not possible due to the geometric constraints imposed by the short alkyl chain. Therefore, good enantioselectivity is expected only for the polymers with longer alkyl chains. The same feature was also observed according to the results shown in Ref. 4. In the light of these results we think that the complex between the polymer and titanium is intramolecular, (a) Turbomole 96.0/4.0.0 User Guide, September 1996, San Diego: Molecular Simulations, 1996. (b) Discover 96.0/4.0.0 User Guide, September 1996, San Diego: Molecular Simulations, 1996. The pcff force field used in the calculations was modified to fit the torsional behaviour of some model molecules at the MP2/6-31G(d) level of theory. Details of the modifications will be described elsewhere (Korpelainen, V.; Ahjopalo, L.; Mannfors, B.; Pietilä, L. O. in preparation).