Stereocontrol in organic synthesis using silicon-containing compounds. A synthesis of the (±)-Prelog–Djerassi lactone

Abstract

Each of the relative stereochemical relationships present in the Prelog–Djerassi lactone 34 was set up by a stereocontrolled reaction based on the presence of a silyl group. These were the enolate protonation 3→4 of a β-silyl ester, the enolate alkylation 11→12 of a β-silyl ester, silyl-to-hydroxy conversion with retention of configuration 13→14, and stereospecifically anti protodesilylation of the allylsilanes 26 and 27 giving largely the alkene 28. These allylsilanes had themselves been prepared in a stereocontrolled, convergent synthesis from the allylic acetates 24 and 25, providing thereby a general solution to the controlled synthesis of a new stereogenic centre relative to a resident centre without regard to their distance apart, except insofar as it influences a necessary separation of diastereoisomers (18 and 19 in this case). Using the opposite double bond geometries, the allylic acetates 29 and 30 gave the complementary pair of allylsilanes 31 and 32, which underwent stereospecifically anti protodesilylation to give largely the alkene 33 diastereoisomeric to 28 at C-6. The alkenes 28 and 33 were converted into the Prelog–Djerassi lactonic acid 34 and its C-6 epimer 35, respectively.

References

1. S. F. Martin and D. E. Guinn, Synthesis, 1991, 245.
2. N. Ouvrard, J. Rodriguez and M. Santelli, Tetrahedron Lett., 1993, 34, 1149; C. Santelli-Rouvier, S. Lefrère and M. Santelli, Tetrahedron Lett., 1994, 35, 6101; M. Miyashita, M. Hoshimo, A. Yoshikoshi, K. Kawamine, K. Yoshihara and H. Irie, Chem. Lett., 1992, 1101.
3. H.-F. Chow and I. Fleming, Tetrahedron Lett., 1985, 26, 397.
4. I. Fleming and N. K. Terrett, J. Chem. Soc., Perkin Trans. 1, 1998, 2645.
5. R. A. N. C. Crump, I. Fleming, J. H. M. Hill, D. Parker, N. L. Reddy and D. Waterson, J. Chem. Soc., Perkin Trans. 1, 1992, 3277.
6. I. Fleming, R. Henning, D. C. Parker, H. E. Plaut and P. E. J. Sanderson, J. Chem. Soc., Perkin Trans. 1, 1995, 317.
7. I. Fleming and N. K. Terrett, J. Organomet. Chem., 1984, 264, 99.
8. T. Mukaiyama and A. Ishida, Chem. Lett., 1975, 319, 1201 and 1977, 467.
9. I. Fleming, J. Goldhill and I. Paterson, Tetrahedron Lett., 1979, 3205 and 3209.
10. I. Fleming and T. V. Lee, Tetrahedron Lett., 1981, 22, 705.
11. J. L. Herrmann, G. R. Kieczykowski and R. H. Schlessinger, Tetrahedron Lett., 1973, 2433.
12. I. Fleming and C. P. Leslie, J. Chem. Soc., Perkin Trans. 1, 1996, 1197.
13. I. Fleming, Chemtracts: Org. Chem., 1996, 9, 1; G. R. Jones and Y. Landais, Tetrahedron, 1996, 37, 7599; K. Tamao, Adv. Silicon Chem., JAI Press, Greenwich, CT, 1996, 3, 1.
14. A. Barbero, D. C. Blakemore, I. Fleming and R. N. Wesley, J. Chem. Soc., Perkin Trans. 1, 1997, 1329.
15. I. Fleming and N. K. Terrett, J. Organomet. Chem., 1984, 264, 99.
16. I. Fleming and A. Pearce, J. Chem. Soc., Perkin Trans. 1, 1981, 251; H.-F. Chow and I. Fleming, J. Chem. Soc., Perkin Trans. 1, 1984, 1815.
17. I. Fleming and D. Marchi, Synthesis, 1981, 560.
18. I. Fleming, D. Marchi and S. K. Patel, J. Chem. Soc., Perkin Trans. 1, 1981, 2518.
19. I. Fleming, P. E. J. Sanderson and N. K. Terrett, Synthesis, 1992, 69.
20. I. Fleming, N. J. Lawrence, A. K. Sarkar and A. P. Thomas, J. Chem. Soc., Perkin Trans. 1, 1992, 3303.
21. For another example, see P. Mohr, Tetrahedron Lett., 1995, 36, 7221.
22. Y. Landais and L. Parra-Rapado, Tetrahedron Lett., 1996, 37, 1209 see also R. Angelaud and Y. Landais, Tetrahedron Lett., 1997, 38, 8841; R. Angelaud, Y. Landais and L. Parra-Rapado, Tetrahedron Lett., 1997, 38, 8845.
23. A. Claesson and L.-I. Olsson, J. Am. Chem. Soc., 1979, 101, 7302 and references therein A. Burger, J.-P. Roussel, C. Hetru, J. A. Hoffmann and B. Luu, Tetrahedron, 1989, 45, 155; J. K. Crandall, D. J. Keyton and J. Kohne, J. Org. Chem., 1968, 33, 3655; L. G. Damm, M. P. Hartshorn and J. Vaughan, Aust. J. Chem., 1976, 29, 1017; M. P. Hartshorn, R. S. Thompson and J. Vaughan, ibid., 1977, 30, 865; J. W. Blunt, M. P. Hartshorn, M. H. G. Munroe, L. T. Soong, R. S. Thompson and J. Vaughan, J. Chem. Soc., Chem. Commun., 1980, 820; C. J. Elsevier, J. Meijer, H. Westmijze, P. Vermeer and L. A. Van Dijk, J. Chem. Soc., Chem. Commun., 1982, 84 and references therein I. Fleming, Y. Landais and P. R. Raithby, J. Chem. Soc., Perkin Trans. 1, 1991, 715.
24. S. Masamune, C. U. Kim, K. E. Wilson, G. O. Spessard, P.-E. Georghiou and G. S. Bates, J. Am. Chem. Soc., 1975, 97, 3512.
25. J. D. White and Y. Fukuyama, J. Am. Chem. Soc., 1979, 101, 226.
26. G. Stork and V. Nair, J. Am. Chem. Soc., 1979, 101, 1315.
27. P. A. Bartlett and J. L. Adams, J. Am. Chem. Soc., 1981, 102, 337.
28. R. E. Ireland and J. P. Daub, J. Org. Chem., 1981, 46, 479.
29. P. A. Grieco, Y. Ohfune, Y. Yokoyama and W. Owens, J. Am. Chem. Soc., 1979, 101, 4749; M. Isobe, Y. Ichikawa and T. Goto, Tetrahedron Lett., 1981, 22, 4287; S. Masamune, Aldrichimica Acta, 1978, 11, 23; S. Masamune, M. Hirama, S. Mori, S. A. Ali and D. S. Garvey, J. Am. Chem. Soc., 1981, 103, 1568; K. Maruyama, Y. Ishihara and Y. Yamamoto, Tetrahedron Lett., 1981, 22, 4235; R. H. Schlessinger and M. A. Poss, J. Am. Chem. Soc., 1982, 104, 357; S. Danishefsky, N. Kato, D. Askin and J. F. Kerwin, Jr., J. Am. Chem. Soc., 1982, 104, 360; W. C. Still and K. R. Shaw, Tetrahedron Lett., 1981, 22, 3725; R. W. Hoffmann, H.-J. Zeiss, W. Ladner and S. Tabche, Chem. Ber., 1982, 115, 2357; D. A. Evans and J. Bartroli, Tetrahedron Lett., 1982, 23, 807.
30. D. J. Morgans, Jr., Tetrahedron Lett., 1981, 22, 3721.