Stereochemical assignment of the enantiomers of omeprazole from X-ray analysis of a fenchyloxymethyl derivative of (+)-(R)-omeprazole

Tetrahedron Asymmetry

Volumn 8, Issue 12, 1997, Pages 1967-1970

  Von Unge, Sverker ^a   Langer, Vratislav ^b   Sjölin, Lennart ^b  

^a ASTRAZENECA R AND D   (Sweden)

^b CHALMERS UNIVERSITY OF TECHNOLOGY   (Sweden)

Author keywords

[No Author keywords available]

Indexed keywords

OMEPRAZOLE; OMEPRAZOLE DERIVATIVE;

ARTICLE; DRUG SYNTHESIS; ENANTIOMER; PRIORITY JOURNAL; STEREOCHEMISTRY; STEREOISOMERISM; X RAY ANALYSIS; X RAY CRYSTALLOGRAPHY;

EID: 0031008015     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0957-4166(97)00195-X     Document Type: Article

References (21)

1. Lindberg, P.; Brändström, A.; Wallmark, B.; Mattsson, H.; Rikner, L.; Hoffman, K.-J.; Med. Res. Rev., 1990, 10, 1-54.
2. Fellenius, E.; Berglindh, T.; Sachs, G.; Olbe, L.; Elander, B.; Sjöstrand, S.-E.; Wallmark, B.; Nature (London), 1981, 290, 159-161.
3. Allenmark, S.; Bomgren, B.; Borén, H.; Lagerström, P.-O.; Anal. Biochem., 1984, 136, 293-297.
4. Erlandsson, P.; Isaksson, R.; Lorentzon, P.; Lindberg, P.; J. Chromatogr., 1990, 532, 305-319.
5. Kohl, B.; Senn-Bilfinger, J.; Patent appl. DE 4035455. (Priority date: November 8, 1990.)
6. Lindberg, P.; von Unge, S.; Patent appl. WO 94/27988. (Priority date: May 28, 1993.)
7. Larsson, M.; Stenhede, U.; Sörensen, H.; von Unge, S.; Cotton H.; Patent appl. WO 96/02535. (Priority date: July 15, 1994.)
8. Cairns, A. M.; Chiou, R. H.-Y.; Rogers, J. D.; Demetriades, J. L.; J. Chromatogr. B., 1995, 666, 323-328.
9. Karlsson, A.; Hermansson, S.; Chromatographia., 1997, 44, 10-18.
10. Katsuki H.; Yagi, H.; Arimori, K.; Nakamura, C.; Nakano, M.; Katafuchi, S.; Fujioka, Y.; Fujiyama, S.; Pharmaceut. Res., 1996, 13, 611-615.
11. Tanaka, M.; Yamazaki, H.; Anal. Chem., 1996, 68, 1513-1516.
12. Uematsu, T.; Nakano, M.; Kosuge, K.; Nagai, A.; Sato, A.; Nakashima, M.; J. Pharmaceut. Sci. 1994, 83, 1407-1411.
13. (1R-endo)-2-(Chloromethoxy)-1,3,3-trimethylbicyclo[2.2.1]heptane 2 was derived from (1R-endo)-(+)-fenchyl alcohol (Aldrich) according to the method described by Shipov, A. G.; Savostyanova, I. A.; Baukov, Y. I., Zh. Obshch. Khim. 1989, 59, 1204-1205.
14. (+)-(K)-1 was synthesized from the corresponding prochiral sulfide by a titanium catalyzed asymmetric oxidation (see reference 7).
15. Alkylation of (+)-(R)-1 with 2 was performed as described in reference 5 except that (+)-(R)-1 was used instead of racemic 1.
16. 2), 6.95-6.99 (2H, m, ArH), 7.68 (1H, d, J=9.0, ArH), 8.15 (1H, s, PyH).
17. Hydrolysis of 4 was carried out as described in reference 5. Although omeprazole and omeprazole analogues are acid labile, they are stable in 90% sulfuric acid (see e.g. Senn-Bilfinger, J.; Krüger, U.; Sturm, E.; Figala, V; Klemm, K.; Kohl, B.; Rainer, G.; Schaefer, H.; J. Org. Chem., 1987, 52, 4582-4592).
18. Determination that the omeprazole enantiomers had the same configuration was achieved by chiral HPLC.
19. Brändström, A.; Lindberg, P.; Bergman, N.-Å.; Tekenbergs-Hjelte, L.; Ohlson, K.; Grundevik, I.; Nordberg, P.; Alminger, T.; Acta Chem. Scand., 1989, 43, 587-594.
20. Yamada, S.; Narita, S.; Chem. Pharm. Bull., 1994, 42, 1679-1681.
21. 3).