Protection of Hydroxyl Groups as tert-Butyldimethylsilyl Derivatives

Journal of the American Chemical Society

Volumn 94, Issue 17, 1972, Pages 6190-6191

  Corey, E J ^a   Venkateswarlu, A ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 29644432244     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00772a043     Document Type: Article

References (15)

1. For example: (a) β,β,β-trichloroethyl-based groups, R. B. Woodward, I.K. Heusier, J. Gostelli, P. Naegeli, W. Oppolzer, R. Ramage, S. Ranganathan, and H. Vorburggen, J. Amer. Chem. Soc., 88, 852 (1966);
2. pivaloyloxymethyl, M. Rasmussen and N. J. Leonard, J. Amer. Chem. Soc., 89, 5439 (1967);
3. and (c) 4-methoxy-4-tetrahydropyranyl, C. B. Reese, R. Saffhill, and J. E. Sulston, J. Amer. Chem. Soc., 89, 3366 (1967).
4. E. J. Corey and R. K. Varma, J. Amer. Chem. Soc., 93, 7319 (1971).
5. L. H. Sommer, “Stereochemistry, Mechanism and Silicon,” McGraw-Hill, New York, N. Y., 1965, pp 132, 138.
6. See L. H. Sommer and L. J. Taylor, J. Amer. Chem. Soc., 76, 1030 (1954). In our work this substance was prepared in 70% yield by the dropwise addition of commercial reri-butyllithium in pentane toa 1 M solution of dimethyldichlorosilane (1.15 equiv) in pentane at 0° under nitrogen with stirring, maintenance at 0° for 1.5 hr, and at 25° for 48 hr. Distillation at atmospheric pressure (bp 125°) afforded the pure reagent, mp 92.5°.
7. See (a) A. E. Pierce, “Silylation of Organic Compounds,” Pierce Chemical Co., Rockford, Ill., 1968;
8. C. C. Sweeley, R. Bentley, M. Makita, and W. W. Wells, J. Amer. Chem. Soc., 85, 2497 (1963).
9. Fluoride ion in an aptotic medium is a powerful agent for the cleavage of silyl ethers in general. This technique has been used in a number of instances in these laboratories including the recently described synthesis of (±)-fumagillin; see E. J. Corey and B. B. Snider, J. Amer. Chem. Soc., 94, 2549 (1972).
10. See E. J. Corey, T. K. Schaaf, W. Huber, U. Koelliker, and N. M. Weinshenker, J. Amer. Chem. Soc., 92, 397 (1970).
11. E. J. Corey, S. M. Albonico, U. Koelliker, T. K. Schaaf, and R. K. Varma, J. Amer. Chem. Soc., 93, 1491 (1971);
12. E. J. Corey, H. Shirahama, H. Yamamoto, S. Terashima, A. Venkateswarlu, and T. K. Schaaf, J. Amer. Chem. Soc., 93, 1490 (1971).
13. D. L. Fowler, W. V. Loebenstein, D. B. Pall, and C. A. Kraus, J. Amer. Chem. Soc., 62, 1140 (1940). The reagent employed in this work was prepared by neutralization of a 10% aqueous solution of tetra-M-butylammonium hydroxide with 48% hydrofluoric acid, concentration under reduced pressure, drying by azeotropic distillation under reduced pressure using several portions of benzene-acetonitrile (1:1), and final drying at 30° and 0.5 mm for 20 hr.
14. See J. Hayami, N. Ono, and A. Kaji, Tetrahedron Lett., 1385 (1968).
15. See E. J. Corey and T. Ravindranathan, J. Amer. Chem. Soc., 94, 4013 (1972).