Regiocontrolled acylation of myo-inositol orthoformate

Tetrahedron Letters

Volumn 39, Issue 28, 1998, Pages 5085-5088

  Flores Mosquera, María ^a   Martín Lomas, Manuel ^a   Chiara, Jose Luis ^b  

^a INSTITUTO DE INVESTIGACIONES QUÍMICAS   (Spain)

^b INSTITUTO DE QUÍMICA ORGÁNICA GENERAL   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

FORMIC ACID DERIVATIVE; INOSITOL DERIVATIVE;

ACYLATION; ARTICLE; ESTERIFICATION; HYDROLYSIS; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0032499985     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)00911-3     Document Type: Article

References (33)

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4. 2. Mato, J. M. Cell Signal 1989, 1, 143-146. Kilgour, E Cell Signal 1993, 3, 97-105. Gaulton, G. N.; Pratt, J. C. Seminars in Inmunology 1994, 6, 97-104. Rademacher, T. M.; Caro, H.; Kunjara, S.; Wang, D. Y.; Greenbaum, A. L.; MacLean, P. Braz. J. Med. Biol. Res. 1994, 27, 327-341. Field, M. C. Glycobiology 1997, 7, 161-168.
5. 2. Mato, J. M. Cell Signal 1989, 1, 143-146. Kilgour, E Cell Signal 1993, 3, 97-105. Gaulton, G. N.; Pratt, J. C. Seminars in Inmunology 1994, 6, 97-104. Rademacher, T. M.; Caro, H.; Kunjara, S.; Wang, D. Y.; Greenbaum, A. L.; MacLean, P. Braz. J. Med. Biol. Res. 1994, 27, 327-341. Field, M. C. Glycobiology 1997, 7, 161-168.
6. 2. Mato, J. M. Cell Signal 1989, 1, 143-146. Kilgour, E Cell Signal 1993, 3, 97-105. Gaulton, G. N.; Pratt, J. C. Seminars in Inmunology 1994, 6, 97-104. Rademacher, T. M.; Caro, H.; Kunjara, S.; Wang, D. Y.; Greenbaum, A. L.; MacLean, P. Braz. J. Med. Biol. Res. 1994, 27, 327-341. Field, M. C. Glycobiology 1997, 7, 161-168.
7. 2. Mato, J. M. Cell Signal 1989, 1, 143-146. Kilgour, E Cell Signal 1993, 3, 97-105. Gaulton, G. N.; Pratt, J. C. Seminars in Inmunology 1994, 6, 97-104. Rademacher, T. M.; Caro, H.; Kunjara, S.; Wang, D. Y.; Greenbaum, A. L.; MacLean, P. Braz. J. Med. Biol. Res. 1994, 27, 327-341. Field, M. C. Glycobiology 1997, 7, 161-168.
8. 3. Jaramillo, C; Chiara, J. L.; Martín-Lomas, M. J. Org. Chem. 1994, 59, 3135-3141, and references cited therein. Flores, M.; Khiar, N.; Alonso, I.; Moreno, L; Martín-Lomas, M.; Chiara, J. L. VIII European Carbohydrate Symposium, Sevilla, 1995, Abstract A-108. Dietrich, H.; Chiara, J. L.; Martín-Lomas, M. XVII International Carbohydrate Symposium, Milan, 1996, Abstract BP208.
9. 3. Jaramillo, C; Chiara, J. L.; Martín-Lomas, M. J. Org. Chem. 1994, 59, 3135-3141, and references cited therein. Flores, M.; Khiar, N.; Alonso, I.; Moreno, L; Martín-Lomas, M.; Chiara, J. L. VIII European Carbohydrate Symposium, Sevilla, 1995, Abstract A-108. Dietrich, H.; Chiara, J. L.; Martín-Lomas, M. XVII International Carbohydrate Symposium, Milan, 1996, Abstract BP208.
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19. 11. The intrinsic polarity of triol 1 greatly narrowed the range of solvents that could be used in this study.
20. 12. A two-fold excess of 1 was used to minimize formation of diester (±)-4.
21. 6) δ 8.14-8.09 (m, 2H), 7.70-7.34 (m, 3H), 5.77 (ddd, J = 1.7, 1.7, 1.3 Hz, 1H), 5.71 (m, 1H), 5.66 (d, J = 1.3 Hz, 1H), 5.10 (br. d, J = 4.2 Hz, 1H), 4.69 (m, 1H), 4.62 (m, 2H), 4.46 (m, 1H).
22. 14. No diaxial dibenzoate was formed in a detectable amount under any of the conditions tested.
23. 15. An aliquot of the crude reaction mixture was derivatized by treatment with N,O-Bis(trimethylsilyl)-trifluoroacetamide/TMSCl in pyridine at 60 °C for 2h.
24. 16. It should be noted that formation of 3 is favored by entropic factors. Thus, if the axial and equatorial hydroxyls of 1 had comparable reactivities, a 2:1 axial/equatorial ratio of monobenzoates should be expected.
25. 17. For a previous report on the effect of the steric hindrance of the base on the selectivity of acylation reactions see: Ishihara, K.; Kurihara, H.; Yamamoto, H. J. Org. Chem. 1993, 58, 3791.
26. 18. For a general discussion on the relative reactivity of hydroxyl groups towards acid chlorides and acid anhydrides and the factors influencing the regioselectivity, see: (a) Haines, A. H. Adv. Carbohydr. Chem. Biochem. 1976, 53, 11.
27. See also: (b) Box, V. G. S. Heterocycles 1983, 20, 1641.
28. 19. OH-2, being equatorial with respect to the cyclohexane ring and axial with respect to a 1,3-dioxane ring, is the less sterically hindered hydroxyl.
29. 17
30. 5,9 The higher acidity of the axial hydroxyls follows their higher H-bonding character.
31. 9
32. 5.
33. 24. For a very recent example using 2 equivalents of a chiral acylating reagent see: Riley, A. M.; Mahon, M. F.; Potter, B. V. L. Angew. Chem. Int. Ed. Engl. 1997, 36, 1472.