Asymmetric synthesis of esomeprazole
10.1016/s0957-4166(00)00352-9
Crossref journal-article
Elsevier BV
Tetrahedron: Asymmetry (78)
Bibliography

Cotton, H., Elebring, T., Larsson, M., Li, L., Sörensen, H., & von Unge, S. (2000). Asymmetric synthesis of esomeprazole. Tetrahedron: Asymmetry, 11(18), 3819–3825.

Authors 6
  1. Hanna Cotton (first)
  2. Thomas Elebring (additional)
  3. Magnus Larsson (additional)
  4. Lanna Li (additional)
  5. Henrik Sörensen (additional)
  6. Sverker von Unge (additional)
References 19 Referenced 235
  1. 10.1002/med.2610100102 / Med. Res. Rev. by Lindberg (1990)
  2. 10.1038/290159a0 / Nature (Lond.) by Fellenius (1981)
  3. The stereochemical assignment of the enantiomers of omeprazole is described in von Unge, S.; Langer, V.; Sjölin, L. Tetrahedron: Asymmetry 1997, 8, 1967–1970. (10.1016/S0957-4166(97)00195-X)
  4. The enantiomers of omeprazole have previously been isolated by resolution procedures, see: (a) Erlandsson, P.; Isaksson, R.; Lorentzon, P.; Lindberg, P. J. Chromatogr. 1990, 532, 305–319. (b) Kohl, B.; Senn-Bilfinger, J. Patent appl. DE 4035455 (Priority date: November 8, 1990). (c) Lindberg, P.; von Unge, S. Patent appl. WO 94/27988 (Priority date: May 28, 1993). (10.1016/S0378-4347(00)83781-0)
  5. Sulphide 1 is a key intermediate in the production of racemic omeprazole. The synthesis of 1 is described in Carlsson, E. I.; Junggren, U. K.; Larsson, H. S.; von Wittken Sundell, G. W. Patent appl. EP 074341. (Priority date: August 13, 1981).
  6. (a) Davis, F. A.; Sheppard, A. C. Tetrahedron 1989, 45, 5703–5742. (b) Davis, F. A.; Reddy, R. T.; Weismiller, M. C. J. Am. Chem. Soc. 1989, 111, 5964–5965. (c) Davis, F. A.; Reddy, R. T.; Han, W.; Carroll, P. J. J. Am. Chem. Soc. 1992, 114, 1428–1437. (10.1016/S0040-4020(01)89102-X)
  7. The chiral oxidant used was (3′S,2R)-(−)-N-(phenylsulphonyl)-(3,3-dichlorocamphoryl)oxaziridine. Its synthesis is described in Ref. 6c.
  8. von Unge, S. Patent appl. WO 97/02261 (Priority date: July 3, 1995).
  9. For recent reviews see: (a) Kagan, H. B.; Diter, P. Organosulfur Chem. 1998, 2, 1–39. (b) Kagan, H. B. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; Wiley–VCH: New York, 2000; Chapter 6C, pp. 327–356. (10.1016/S1099-8268(98)80004-8)
  10. Although the Sharpless reagent for asymmetric epoxidation of allylic alcohols (see Ref. 11) affords little or no enantioselectivity when used in the oxidation of prochiral sulphides, two groups have independently developed modifications of the reagent that enantioselectively oxidise certain sulphides. Kagan and co-workers obtained aryl methyl sulphoxides with high enantiomeric excess by employing Ti(OiPr)4/DET/ROOH (R=tert-butyl or cumyl) in a ratio of 1:2:1 in the presence of one crucial equivalent of water; see: (a) Pitchen, P.; Duñach, E.; Deshmukh, M. N.; Kagan, H. B. J. Am. Chem. Soc. 1984, 106, 8188–8193. (b) Zhao, S. H.; Samuel, O.; Kagan, H. B. Tetrahedron 1987, 43, 5135–5144. On the other hand, Modena and co-workers achieved comparable results for analogous substrates using Ti(OiPr)4, DET and t-BuOOH in the absence of water but by increasing the amount of DET; see: (c) Di Furia, F.; Modena, G.; Seraglia, R. Synthesis 1984, 325–326. (10.1021/ja00338a030)
  11. (a) Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc. 1980, 102, 5974–5976. (b) Rossiter, B. E.; Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 464–465. (10.1021/ja00538a077)
  12. Kagan and co-workers have for instance demonstrated that the enantiomeric excess for p-tolyl methyl sulphoxide is dramatically decreased when less than 50 mol% of Ti-catalyst is being used (see Ref. 10b).
  13. As opposed to the allylic alcohols employed in the Sharpless asymmetric epoxidation procedure, prochiral sulphides employed in asymmetric sulphoxidations using a modified Sharpless reagent are considered to be non-functional substrates. Thus, the enantioselectivity in these reactions is regarded to be derived mainly from the steric effects of the prochiral sulphide, i.e. by having a large difference in the size of the substituents attached to sulphur; see: (a) Kagan, H. B.; Rebiere, F. Synlett 1990, 643–650. (b) Pitchen, P.; France, C. J.; McFarlane, I. M.; Newton, C. G.; Thompson, D. M. Tetrahedron Lett. 1994, 35, 485–488. (c) Pitchen, P. Chem. Ind. 1994, 636–639.
  14. Chemists at Hoffmann-La Roche have reported that Kagan's original method indeed could be used for the synthesis of the enantiomers of the omeprazole analogue Ro 18-5364 with a modest enantiomeric excess of the crude product (30%); see: Sigrist-Nelson, K.; Krasso, A.; Müller, R. K. M.; Fischli, A. E. Eur. J. Biochem. 1987, 166, 453–459. However, we were not able to reproduce this result in this study (see: Ref. 15). (10.1111/j.1432-1033.1987.tb13537.x)
  15. For further experimental procedures, see: Larsson, E. M.; Stenhede, U. J.; Sörensen, H.; von Unge, P. O. S.; Cotton, H. K. Patent appl. WO 96/02535 (Priority date: July 15, 1994).
  16. Kagan and co-workers have shown that control of temperature as well as the reaction time in the premixing of Ti(OiPr)4, DET and water is necessary in order to ensure high ee's in asymmetric oxidations of different sulphides; see: (a) Diter, P.; Samuel, O.; Taudien, S.; Kagan, H. B. Tetrahedron: Asymmetry 1994, 4, 549–552. (b) Brunel, J.-M.; Diter, P.; Duetsch, M.; Kagan, H. B. J. Org. Chem. 1995, 60, 8086–8088.
  17. The choice of solvent has been reported earlier to have a pronounced influence on the enantiomeric excess of sulphoxides obtained by Kagan's original method; see e.g.: Kagan, H. B.; Duñach, E.; Nemecek, C.; Pitchen, P.; Samuel, O.; Zhao, S.-H. Pure Appl. Chem. 1985, 57, 1911–1916. (10.1351/pac198557121911)
  18. In general, a temperature lower than −20°C during the asymmetric oxidation of sulphides by Kagan's method has proven to be beneficial for the enantioselectivity (see Ref. 13a).
  19. 10.1021/jo960359z / J. Org. Chem. by Di Furia (1996)
Dates
Type When
Created 23 years, 1 month ago (July 25, 2002, 10:45 a.m.)
Deposited 5 years, 7 months ago (Jan. 9, 2020, 12:29 p.m.)
Indexed 1 month, 3 weeks ago (July 2, 2025, 2:11 p.m.)
Issued 24 years, 11 months ago (Sept. 1, 2000)
Published 24 years, 11 months ago (Sept. 1, 2000)
Published Print 24 years, 11 months ago (Sept. 1, 2000)
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@article{Cotton_2000, title={Asymmetric synthesis of esomeprazole}, volume={11}, ISSN={0957-4166}, url={http://dx.doi.org/10.1016/s0957-4166(00)00352-9}, DOI={10.1016/s0957-4166(00)00352-9}, number={18}, journal={Tetrahedron: Asymmetry}, publisher={Elsevier BV}, author={Cotton, Hanna and Elebring, Thomas and Larsson, Magnus and Li, Lanna and Sörensen, Henrik and von Unge, Sverker}, year={2000}, month=sep, pages={3819–3825} }