Synthesis and characterisation of optically active spiro[4.5]decanes

Abstract

The synthesis of spiro[4.5]decanes through a Diels–Alder cycloaddition between 5-methylenefuran-2(5H )-one (protoanemonin) 8, and chiral dienes 1-[(–)-menthyloxy]-3-trimethylsilyloxybuta-1,3-diene, 5, 1-[(–)-bornyloxy]-3-trimethylsilyloxybuta-1,3-diene, 6, and 1-[(+)-isopinocampheyloxy]-3-trimethylsilyloxybuta-1,3-diene, 7, is reported for the first time. Diastereofacial selectivity together with the preference for an endo/exo attack are examined. The effect on the diastereofacial selectivity of substituting dienophile 8 by 3-acetoxy-5-methylenefuran-2(5H )-one 18 is also discussed. The use of Lewis acids as catalysts to enhance selectivity has been attempted without success.

References

1. H. Avcibasi, H. Anil and M. Toprak, Phytochemistry, 1987, 26, 2852.
2. (a) Y. Hashidoko, S. Tahara and J. Mitzutani, J. Chem. Soc., Perkin Trans. 1, 1991, 211; (b) Y. Hashidoko, S. Tahara and J. Mitzutani, Agric. Biol. Chem., 1991, 55, 1049; (c) Y. Hashidoko, S. Tahara and J. Mitzuani, Phytochemistry, 1991, 30, 3729.
3. B. H. Joerg, H. Becker, N. S. Allen and M. P. Gupta, Phytochemistry, 1991, 30, 3043.
4. M. Planas, C. Segura, M. Ventura and R. M. Ortuño, Synth. Commun., 1994, 24, 651.
5. M. Heras, M. Planas, S. Rafel, M. Ventura, J. Font and R. M. Ortuño, An. Quím., Int. Ed., 1996, 92, 233.
6. (a) For the first example of a non-racemic dienophile used in the Diels–Alder reaction, see: H. M. Walborsky, L. Barash and T. C. Davis, J. Org. Chem., 1961, 26, 4778; (b) For a review dealing with non-racemic dienophiles, see: H. B. Kagan and R. Olivier, Chem. Rev., 1992, 92, 1007.
7. (a) For the first example of a non-racemic diene used in the Diels–Alder reaction, see: S. David, J. Eustache and A. Lubineau, J. Chem. Soc., Perkin Trans. 1, 1974, 2274; (b) For a review which cites several articles dealing with non-racemic dienes, see ref. 6(b) and M. J. Tashner, in Organic Synthesis: Theory and Application, vol. 1; ed. T. Hudlicky, JAI Press, Greenwich, 1989, pp. 1–101; (c) For examples of a non-racemic diene in reaction with nitro olefines, see: D. Enders, O. Meyer and G. Raabe, Synthesis, 1992, 1242; G. Raabe and J. Runsink, Synthesis, 1994, 66.
8. (a) B. M. Trost, D. O'Krongly and J. L. Belletire, J. Am. Chem. Soc., 1980, 102, 7595; (b) R. C. Gupta, P. A. Harland and R. J. Stoodley, J. Chem. Soc., Chem. Commun., 1983, 754.
9. R. C. Gupta, P. A. Harland and R. J. Stoodley, Tetrahedron, 1984, 40, 4657.
10. R. C. Gupta, M. Z. Slawin, R. J. Stoodley and D. J. Williams, J. Chem. Soc., Chem. Commun., 1986, 668.
11. M. Bednarski and S. Danishefsky, J. Am. Chem. Soc., 1986, 108, 7060.
12. E. Shaw, J. Am. Chem. Soc., 1946, 68, 2510.
13. S. Danishefsky, M. Bednarski, T. Izawa and C. Maring, J. Org. Chem., 1984, 49, 2290.
14. (a) S. V. Attwood and A. G. M. Barrett, J. Chem. Soc., Perkin Trans. 1, 1984, 1315; (b) A. G. M. Barrett and H. G. Sheth, J. Org. Chem., 1983, 48, 5017.