Site selectivity in the α-silyl lithiation of 3,4,6-tris-O-(tert-butyldimethylsilyl)-D-glucal and 3,4-bis-O-(tert-butyldimethylsilyl)-6-deoxy-L-glucal with tert-butyllithium

Journal of Organic Chemistry

Volumn 61, Issue 3, 1996, Pages 1165-1168

  Friesen, Richard W ^a   Trimble, Laird A ^a  

^a MERCK FROSST CENTRE FOR THERAPEUTIC RESEARCH   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000234563     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9517003     Document Type: Article

References (34)

1. (a) Nicolaou, K. C.; Hwang, C.-K.; Duggan, M. E. J. Chem. Soc., Chem. Commun. 1986, 925.
2. (b) Hanessian, S.; Martin, M.; Desai, R. C. J. Chem. Soc., Chem. Commun. 1986, 926.
3. (c) Lesimple, P.; Beau, J.-M.; Jaurand, G.; Sinay, P. Tetrahedron Lett. 1986, 27, 6201.
4. (d) Friesen, R. W.; Sturino, C. F. J. Org. Chem. 1990, 55, 2572.
5. (e) Dubois, E.; Beau, J.-M. Tetrahedron Lett. 1990, 31, 5165.
6. (f) Dubois, E.; Beau, J.-M. J. Chem. Soc., Chem. Commun. 1990, 1191.
7. (g) Tius, M. A.; Gomez-Galeno, J.; Gu, X.; Zaidi, J. H. J. Am. Chem. Soc. 1991, 113, 5775.
8. (h) Parker, K. A.; Coburn, C. A. J. Am. Chem. Soc. 1991, 113, 8516.
9. (i) Friesen, R. W.; Loo, R. W.; Sturino, C. F.Can. J. Chem. 1994, 72, 1262.
10. (a) Boeckman, R. K., Jr.; Bruza, K. J. Tetrahedron Lett. 1977, 4187.
11. (b) Boeckman, R. K., Jr.; Bruza, K J. Tetrahedron 1981, 23, 3997.
12. Friesen, R. W.; Sturino, C. F.; Daljeet, A. K.; Kolaczewska, A. E. J. Org. Chem. 1991, 56, 1944.
13. Although the silyl moiety is commonly viewed as an alcohol protecting group that is relatively stable under basic reaction conditions, metalation α to silicon is a fairly well-known reaction process. For some leading references, see: (a) Peterson, D. J. J. Organomet. Chem. 1967, 9, 373. (b) Gornowicz, G. A.; West, R. J. Am. Chem. Soc. 1968, 90, 4478. (c) West, R.; Gornowicz, G. A. J. Organomet. Chem. 1971, 28, 25. (d) Wright, A.; West, R. J. Am. Chem. Soc. 1974, 96, 3214. (e) MacDonald, J. E.; Poindexter, G. S. Tetrahedron Lett. 1987, 28, 1851.
14. Although the silyl moiety is commonly viewed as an alcohol protecting group that is relatively stable under basic reaction conditions, metalation α to silicon is a fairly well-known reaction process. For some leading references, see: (a) Peterson, D. J. J. Organomet. Chem. 1967, 9, 373. (b) Gornowicz, G. A.; West, R. J. Am. Chem. Soc. 1968, 90, 4478. (c) West, R.; Gornowicz, G. A. J. Organomet. Chem. 1971, 28, 25. (d) Wright, A.; West, R. J. Am. Chem. Soc. 1974, 96, 3214. (e) MacDonald, J. E.; Poindexter, G. S. Tetrahedron Lett. 1987, 28, 1851.
15. Although the silyl moiety is commonly viewed as an alcohol protecting group that is relatively stable under basic reaction conditions, metalation α to silicon is a fairly well-known reaction process. For some leading references, see: (a) Peterson, D. J. J. Organomet. Chem. 1967, 9, 373. (b) Gornowicz, G. A.; West, R. J. Am. Chem. Soc. 1968, 90, 4478. (c) West, R.; Gornowicz, G. A. J. Organomet. Chem. 1971, 28, 25. (d) Wright, A.; West, R. J. Am. Chem. Soc. 1974, 96, 3214. (e) MacDonald, J. E.; Poindexter, G. S. Tetrahedron Lett. 1987, 28, 1851.
16. Although the silyl moiety is commonly viewed as an alcohol protecting group that is relatively stable under basic reaction conditions, metalation α to silicon is a fairly well-known reaction process. For some leading references, see: (a) Peterson, D. J. J. Organomet. Chem. 1967, 9, 373. (b) Gornowicz, G. A.; West, R. J. Am. Chem. Soc. 1968, 90, 4478. (c) West, R.; Gornowicz, G. A. J. Organomet. Chem. 1971, 28, 25. (d) Wright, A.; West, R. J. Am. Chem. Soc. 1974, 96, 3214. (e) MacDonald, J. E.; Poindexter, G. S. Tetrahedron Lett. 1987, 28, 1851.
17. Although the silyl moiety is commonly viewed as an alcohol protecting group that is relatively stable under basic reaction conditions, metalation α to silicon is a fairly well-known reaction process. For some leading references, see: (a) Peterson, D. J. J. Organomet. Chem. 1967, 9, 373. (b) Gornowicz, G. A.; West, R. J. Am. Chem. Soc. 1968, 90, 4478. (c) West, R.; Gornowicz, G. A. J. Organomet. Chem. 1971, 28, 25. (d) Wright, A.; West, R. J. Am. Chem. Soc. 1974, 96, 3214. (e) MacDonald, J. E.; Poindexter, G. S. Tetrahedron Lett. 1987, 28, 1851.
18. For general discussions of deprotonation α to silicon, see: (f) Colvin, E. W. Silicon in Organic Synthesis; Butterworths London, 1981; Chapter 4.2. (g) Weber, W. P. Silicon Reagents for Organic Synthesis; Springer-Verlag: Berlin, 1983;Chapter 6.2.D.
19. For general discussions of deprotonation α to silicon, see: (f) Colvin, E. W. Silicon in Organic Synthesis; Butterworths London, 1981; Chapter 4.2. (g) Weber, W. P. Silicon Reagents for Organic Synthesis; Springer-Verlag: Berlin, 1983;Chapter 6.2.D.
20. (a) Boeckman, R. K., Jr.; Charette, A. B.; Asberom, T.; Johnston, B. H. J. Am. Chem. Soc. 1987, 109, 7553.
21. (b) Crich, D.; Ritchie, T. J. Tetrahedron 1988, 44, 2319.
22. (c) Imanieh, H.; Quayle, P.; Voaden, M.; Conway, C.; Street, S. D. A. Tetrahedron Lett. 1992, 33, 543.
23. (d) Zhang, H.-C.; Brakta, M.; Daves, G. D., Jr. Tetrahedron Lett. 1993, 34, 1571.
24. Note that glucal 2 is drawn as its enantiomer for ease of comparison to glucal 1.
25. (a) Paquette, L. A.; Oplinger, J. A. Tetrahedron 1989, 45, 107.
26. (b) Parker, K. A.; Coburn, C. A.; Koh, Y. J. Org. Chem.
27. (a) Emsley, J. W.; Feeney, J.; Sutcliffe, L. H High Resolution Nuclear Magnetic Resonance Spectroscopy; Pergamon Press: Oxford, 1966; Vol. 2, Chapter 12.10.1.
28. (b) Reese, P. B.; Trimble, L. A.; Vederas, J. C. Can. J. Chem. 1986, 64, 1427 and references cited therein.
29. Stott, K.; Stonehouse, J.; Keeler, J.; Hwang, T.-L.; Shaka, A. J. J. Am. Chem. Soc. 1995, 117, 4199.
30. Note that the reference peaks for spectra a and d are different (see footnotes a and b in Table 1). Spectrum d has been aligned with spectrum a (see text), and therefore, the chemical shifts in spectrum d cannot be read from the scale
31. tBuLi and ether exist in a temperature-dependent equilibrium between tetra solvated dimers and unsolvated tetramers, it is the dimer that is the more reactive metalating species. Bates, T. F.; Clarke, M. T.; Thomas, R. D. J. Am. Chem. Soc. 1988, 110, 5109.
32. tBuLi. See, for example: (a) Bates, T. F.; Thomas, R. D. J. Organomet. Chem. 1989, 359, 285.
33. (b) Hosomi, A., Kohra, S ; Tominaga, Y.; Shoji, M.; Sakurai, H. Chem. Pharm Bull. 1987, 35, 1663.
34. See ref 3 for general experimental details.