A synthesis of enantiomerically enriched propargyl silanes

Abstract

Reduction of ethyl 3-methyl-, 3-isopropyl- and 3-n-pentyl-3-[dimethyl(phenyl)silyl]propanoates 4 with DIBAL to the aldehydes 5, enol trifluoromethanesulfonate (triflate) formation using trifluoromethanesulfonic (triflic) anhydride and 2,6-di-tert-butylpyridine, and elimination using LDA, gives the propargyl silanes 8. The esters 4 could also be prepared enantiomerically enriched (11), and the final products are the enantiomerically enriched propargyl (homochiral) silanes 14.

References

1. M. J. C. Buckle, I. Fleming and S. Gil, Tetrahedron Lett., 1992, 33, 4479.
2. M. J. C. Buckle and I. Fleming, Tetrahedron Lett., 1993, 34, 2383.
3. T. Hayashi, Y. Okamoto and M. Kumada, Tetrahedron Lett., 1983, 24, 807.
4. S. Rajagopalan and G. Zweifel, Synthesis, 1984, 111 See also, H. Hommes, H. D. Verkruijsse and L. Brandsma, Recl. Trav. Chim. Pays-Bas, 1980, 99, 113; Y. Makioka, K. Koyama, T. Nishiyama and K. Takaki, Tetrahedron Lett., 1995, 36, 6283.
5. For one other solution, see: M. Shibasaki, Y. Torisawa and S. Ikegami, Tetrahedron Lett., 1982, 23, 4607.
6. P. J. Stang, M. G. Mangum, D. P. Fox and P. Haak, J. Am. Chem. Soc., 1974, 96, 4562.
7. P. J. Stang, J. Davis and D. P. Fox, J. Chem. Soc., Chem. Commun., 1975, 17; P. J. Stang, D. P. Fox, C. J. Collins and C. R. Watson, Jr., J. Org. Chem., 1978, 43, 364.
8. R. A. N. C. Crump, I. Fleming and C. J. Urch, J. Chem. Soc., Perkin Trans. 1, 1994, 701.
9. P. J. Stang and W. Treptow, Synthesis, 1980, 283.
10. I. Fleming and N. D. Kindon, J. Chem. Soc., Perkin Trans. 1, 1995, 303.
11. A. Chénedé, N. Abd. Rahman and I. Fleming, Tetrahedron Lett., 1997, 39, 2381.
12. I. Fleming and U. Ghosh, J. Chem. Soc., Perkin Trans. 1, 1994, 257.
13. W. S. Wadsworth and W. D. Emmons, J. Am. Chem. Soc., 1961, 83, 1733.
14. S. V. Kelkar, A. A. Arbale, G. S. Joshi and G. H. Kilkarni, Synth. Commun., 1990, 839.
15. T. Nakai, T. Mimura and T. Kurokawa, Tetrahedron Lett., 1978, 32, 2895.
16. D. J. Ager, I. Fleming and S. K. Patel, J. Chem. Soc., Perkin Trans. 1, 1981, 2520.
17. A. Barbero, D. C. Blakemore, I. Fleming and R. N. Wesley, J. Chem. Soc., Perkin Trans. 1, 1997, 1329.
18. I. Fleming and T. W. Newton, J. Chem. Soc., Perkin Trans. 1, 1984, 1805.
19. A. K. Sarkar, PhD Thesis, Cambridge, 1988.
20. S. Searles, Y. Li, B. Nassim, M.-T. R. Lopes, P. T. Tran and P. Crabbé, J. Chem. Soc., Perkin Trans. 1, 1984, 747.
21. K. Tomioka, T. Suenaga and K. Koga, Tetrahedron Lett., 1986, 27, 369.
22. C. Kruk and K. Spaargaren, Spectrochim. Acta, Part A, 1971, 27, 77; P.-T. Sou, Bull. Fac. Sci. Univ. Fr. Chin. Peiping, 1934, 1, 1 (Chem. Abstr., 1934, 29, 25197).
23. E. N. Step, V. F. Tarasov and A. L. Buchachenko, Chem. Phys. Lett., 1988, 144, 523.
24. D. L. Comins and A. Dehghani, Tetrahedron Lett., 1992, 33, 6299.
25. I. Fleming and N. J. Lawrence, J. Chem. Soc., Perkin Trans. 1, 1992, 3309.
26. L. Fábry and P. Gomory, Acta Chim. Acad. Sci. Hung, 1981, 106, 291 (Chem. Abstr., 1981, 95, 149 532u).
27. C. Jun and R. H. Crabtree, J. Organomet. Chem., 1993, 447, 177.
28. I. T. Morgan, PhD Thesis, Cambridge, 1991.
29. E. K. Raunio and W. A. Bonner, J. Org. Chem., 1966, 31, 396.
30. C. R. Conard and M. A. Dolliver, Org. Synth., 1943, Coll. Vol. II, 167.
31. N. A. Burditt, M. C. Whiting and L. M. Venanzi, J. Chem. Soc. (C), 1967, 2273.
32. R. J. Hargrove and P. J. Stang, J. Org. Chem., 1974, 39, 581.
33. G. W. Fleet and T. K. M. Shing, Chem. Soc., Chem. Commun., 1983, 849.