Highly Stereoselective Routes to Functionalized Geminal Alkyl Derivatives of Carbohydrates

Journal of Organic Chemistry

Volumn 46, Issue 18, 1981, Pages 3764-3767

  Fraser Reid, Bert ^a   Tsang, Raymond ^a   Tulshian, Deen Bundhu ^a   Sun, King Mo ^a  

^a UNIVERSITY OF MARYLAND   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0141446067     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo00331a050     Document Type: Article

References (19)

1. Supported in part by a research grant from the National Institutes of Health, CA-28192.
2. Ali, Y.; Szarek, W. A. Carbohydr. Res. 1978, 67, C17. Szarek, W. A.; Vyas, D. M.; Chem, L.-Y. Supported in part by a research grant from the National Institutes of Health, CA-28192. 1977, 53, Cl.
3. Trost, H. M.; Bodgdanowicz, M. J. J. Am. Chem. Soc. 1973,95, 2038.
4. Wenkert, E.; Buckwalter, B. L.; Craveiro, A. A.; Sanehez, E. L.; Sathe, S. S. J. Am. Chem. Soc. 1978,100,1267.
5. See, for example, Methods Carbohydr. Chem. 1972, 6, Sect. 3.
6. Corey, E. J.; Shulman, J. I. Methods Carbohydr. Chem. 1970,92, 5522.
7. Tam, T. F.; Fraser-Reid, B. J. Chem. Soc., Chem. Commun. 1980, 556.
8. Jordaan, J. H.; Soredlay, S. Carbohydr. Res. 1971,16,177. Iley, D. E.; Tam, S. Y. K.; Fraser-Reid, B. J. Chem. Soc., Chem. Commun. 1977, 55,193.
9. See, for example; Tronchet, J. M. J.; Tronchet, J. Helo. Chim. Acta 1977,60,1984. Anderson, R. C.; Fraser-Reid, B. J. Am. Chem. Soc. 1975, 97, 3870; Ohrui, H.; Moto, S. E. Tetrahedron Lett. 1975, 3657.
10. For the preparation of ketones 1 and 16, methyl 4,6-O-benzylidene-D-glucopyranoside was treated with 1 equiv of TBDMSiCl. The C2 and C3 silyl ethers were separated by column chromatography and oxidized to 1 and 16, respectively.
11. With the 2-O-benzyl analogue of 1, both geometric isomers of the acrylate ester were produced in equal amounts.
12. This product gave satisfactory NMR spectra and HRMS or analytical data.
13. See, for example: Howarth, G. B.; Szarek, W. A.; Jones, J. K. N. Can. J. Chem. 1974,96,1775; Jordaan, J. H.; Smedley, S. Carbohydr. Res. 1971,16,177; 1971,18, 303.
14. Attempts to prepare the analogue of 1 with the C2 function in axial orientation were unsuccessful, epimerization to 1 occurring spontaneously.
15. Rosenthal, A.; Catsoulacos, P. Can. J. Chem. 1968, 46, 2868.
16. Hanessian, S. Methods Carbohydr. Chem. 1972, 6, 183.
17. Fraser-Reid, B.; Walker, D. L. Methods Carbohydr. Chem. 1980, 58, 2694.
18. Holder of Graduate Fellowship in Chemistry from (a) The Upjohn Company and
19. Merck Sharp and Dohme (Rahway, NJ).