Lipase mediated desymmetrization of meso 2,6-di(acetoxymethyl)-tetrahydropyran-4-one derivatives. An innovative route to enantiopure 2,4,6-trifunctionalized C-glycosides

Tetrahedron Asymmetry

Volumn 7, Issue 10, 1996, Pages 2889-2900

  Lampe, Thomas F J ^a   Hoffmann, H M R ^a   Bornscheuer, Uwe T ^b  

^a LEIBNIZ UNIVERSITY HANNOVER   (Germany)

^b UNIVERSITY OF STUTTGART   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

GLYCOSIDE; TRIACYLGLYCEROL LIPASE;

ARTICLE; CARBOHYDRATE SYNTHESIS; CHIRALITY; DRUG SYNTHESIS; ENZYME ACTIVITY; PRIORITY JOURNAL; REACTION ANALYSIS; TECHNIQUE; X RAY ANALYSIS;

EID: 0030272259     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/0957-4166(96)00380-1     Document Type: Article

References (30)

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10. 4. Prepared on 1 molar scale (55-60 % yield) from furan and 1,1,3,3-tetrabromoacetone via the triethyl borate/zinc procedure and reductive denomination. Hoffmann, H. M. R.; Iqbal, M. N. Tetrahedron Lett., 1975, 16, 4487 and references cited therein. See also Reinecke, J.; Hoffmann, H. M. R. Chem. Eur. J., 1995, 1, 358. Oxabicycle 3 is water soluble and the isolated yield tends to drop on small scale preparation: Hill, A. E.; Greenwood, G.; Hoffmann, H. M. R. J. Am. Chem. Soc., 1973, 95, 1338.
11. 4. Prepared on 1 molar scale (55-60 % yield) from furan and 1,1,3,3-tetrabromoacetone via the triethyl borate/zinc procedure and reductive denomination. Hoffmann, H. M. R.; Iqbal, M. N. Tetrahedron Lett., 1975, 16, 4487 and references cited therein. See also Reinecke, J.; Hoffmann, H. M. R. Chem. Eur. J., 1995, 1, 358. Oxabicycle 3 is water soluble and the isolated yield tends to drop on small scale preparation: Hill, A. E.; Greenwood, G.; Hoffmann, H. M. R. J. Am. Chem. Soc., 1973, 95, 1338.
12. 4. Prepared on 1 molar scale (55-60 % yield) from furan and 1,1,3,3-tetrabromoacetone via the triethyl borate/zinc procedure and reductive denomination. Hoffmann, H. M. R.; Iqbal, M. N. Tetrahedron Lett., 1975, 16, 4487 and references cited therein. See also Reinecke, J.; Hoffmann, H. M. R. Chem. Eur. J., 1995, 1, 358. Oxabicycle 3 is water soluble and the isolated yield tends to drop on small scale preparation: Hill, A. E.; Greenwood, G.; Hoffmann, H. M. R. J. Am. Chem. Soc., 1973, 95, 1338.
13. 5. (a) Lampe, T. F. J.; Hoffmann, H. M. R. Chem. Commun., 1996, 1931;
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15. 6. Use of standard ketalization procedures (cf. Meskens, F. A. J. Synthesis, 1981, 501) caused fragmentation of oxabicyclic ketone 3 and yielded furan derivatives instead of desired ketals.
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17. 8. We later experienced that a pH-stat is not necessary if a 0.5 molar phosphate buffer solution (pH 7) is used in sufficient amount to maintain the pH above 6 (lipase PS is stable and active in a wide pH range).
18. 9. S-MTPA-Cl was prepared from R-MTPA (Fluka, Chira Select®); Dale, J. A.; Mosher, H. S. J. Am. Chem. Soc., 1973, 95, 512.
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27. 14. For structurally similar oxacyclic ketone A Cha et al. have recently reported an enantioselective pro-R acetylation (Amano PS 30, isopropenyl acetate, 76 %, 85 % e.e.) catalysed by lipase from Pseudomonas cepacia (Kim, H.; Ziani-Cherif, C.; Oh, J.; Cha, J. K. J. Org. Chem., 1995, 60, 792). (formula presented) Thus, a changeover from pro-S selectivity (70 % e.e. in 9) to pro-R selectivity (85 % e.e. in A) is observed. The propano bridge in A forces a boat-like oxacyclohexanone moiety with reduced mobility leading to an exposed position of the carbonyl group, whereas 9 should adopt a chair conformation preferentially, but not exclusively.
28. int = 0.0531 over 3324 independent reflections, absolute structure parameter 0.017 (8).
29. 16. A recent application is described elswhere: Lampe, T. F. J; Hoffmann, H. M. R. Tetrahedron Lett. 1996, 37, in press.
30. 2O (74 % yield); cf Bruice, T. C.; Piszkiewicz, D. J. Am. Chem. Soc., 1967, 89, 3568.