Synthesis of the naturally occurring [3.3.3]propellane (±)-modhephene featuring a photocycloaddition–reductive fragmentation diquinane construction

Abstract

Modhephene has been synthesized in 11 steps and 21% overall yield from cyclopentadiene, by a stereoselective route that features a photocycloaddition–fragmentation sequence for the construction of the diquinane core.

References

1. G. Metha and A. Srikrishna, Chem. Rev., 1997, 97, 671.
2. (a) V. H. Rawal and C. Dufour, J. Am. Chem. Soc., 1994, 116, 2613; (b) V. H. Rawal, C. Dufour and A. Eschbach, J. Chem. Soc., Chem. Commun., 1994, 1797; (c) V. H. Rawal, C. Dufour and S. Iwasa, Tetrahedron Lett., 1995, 36, 19; (d) V. H. Rawal, A. Fabre and S. Iwasa, Tetrahedron Lett., 1995, 36, 6851; (e) V. H. Rawal, A. Eschbach, C. Dufour and S. Iwasa, Pure Appl. Chem., 1996, 37, 675; (f) C. Dufour, S. Iwasa, A. Fabre and V. H. Rawal, Tetrahedron Lett., 1996, 37, 7867.
3. Isolation: L. H. Zalkow, R. N. Harris, III and D. Van Derveer, J. Chem. Soc., Chem. Commun., 1978, 420; F. Bohlmann, C. Zdero, R. Bohlmann, R. M. King and H. Robinson, Phytochemistry, 1980, 19, 579.
4. Syntheses: (a) M. Karpf and A. S. Dreiding, Tetrahedron Lett., 1980, 21, 4569; Helv. Chim. Acta, 1981, 64, 1123; (b) A. B. Smith, III and P. J. Jerris, J. Am. Chem. Soc., 1981, 103, 194; J. Org. Chem., 1982, 47, 1845; (c) H. Schostarez and L. A. Paquette, J. Am. Chem. Soc., 1981, 103, 722; Tetrahedron, 1981, 37, 4431; (d) W. Oppolzer and F. Marazza, Helv. Chim. Acta, 1981, 64, 1575; W. Oppolzer and K. Battig, Helv. Chim. Acta, 1981, 64, 2489; (e) P. A. Wender and G. B. Dreyer, J. Am. Chem. Soc., 1982, 104, 5805; (f) J. Wrobel, K. Takahashi, V. Honkan, G. Lannoye, J. M. Cook and S. H. Bertz, J. Org. Chem., 1983, 48, 139; (g) Y. Tobe, S. Yamashita, T. Yamashita, K. Kakiuchi and Y. Odaira, J. Chem. Soc., Chem. Commun., 1984, 1259; (h) D. Wilkening and B. P. Mundy, Tetrahedron Lett., 1984, 25, 4619; B. P. Mundy, D. Wilkening and K. B. Lipkowitz, J. Org. Chem., 1985, 50, 5727; (i) G. Metha and D. Subrahmanyam, J. Chem. Soc., Chem. Commun., 1985, 768; G. Metha and D. Subrahmanyam, J. Chem. Soc., Perkin Trans. 1, 1991, 395; (j) E. A. Marsh, S. K. Math and C. J. Flann, Tetrahedron Lett., 1988, 29, 2147; Tetrahedron, 1989, 45, 4950; (k) L. Fitjer, A. Kanschik and M. Majewski, Tetrahedron Lett., 1988, 29, 5525; L. Fitjer, M. Majewski and A. Kanschik, Tetrahedron Lett., 1988, 29, 1263; (l) C. P. Jasperse and D. P. Curran, J. Am. Chem. Soc., 1990, 112, 5601; (m) C. Sha, T. Jean and D. Wang, Tetrahedron Lett., 1990, 31, 3745; (n) G. A. Kraus and J. Shi, J. Org. Chem., 1990, 55, 5423; J. Org. Chem., 1991, 56, 4147; (o) S. C. Suri, Tetrahedron Lett., 1993, 34, 8321; (p) T. Uyehara, T. Murayama, K. Sakai, M. Ueno and T. Sato, Tetrahedron Lett., 1996, 37, 7295; (q) H. Lee, D. Kim and S. Kim, Chem. Commun., 1996, 1539.
5. The details of this alkylation will be reported in a full paper.
6. General reviews on radical chemistry: D. P. Curran, Synthesis, 1988, 417, 489; D. P. Curran, in Comprehesnive Organic Synthesis, ed. B. M. Trost and I. Fleming, Pergamon Press, Oxford, 1991; vol. 4, pp. 715–777; pp. 779–899; B. Giese, B. Kopping, T. Göbel, J. Dickhut, G. Thoma, K. J. Kulicke and F. Trach, Org. React., 1996, 48, 301.
7. E. J. Corey and M. Chaykovsky, J. Am. Chem. Soc., 1965, 87, 1345; J. S. Swenton, D. K. Anderson, D. K. Jackson and L. Narasimhan, J. Org. Chem., 1981, 46, 4825; K. Ishizumi, N. Ohashi and N. Tanno, J. Org. Chem., 1987, 52, 4477.
8. For an extensive investigation of the reductive fragmentation of simple oxetanes, see B. Mudryk and T. Cohen, J. Org. Chem., 1989, 54, 5657; J. Org. Chem., 1991, 56, 5760For epoxide fragmentations, see: B. Mudryk and T. Cohen, Org. Synth., 1993, 72, 173 and references cited therein.
9. An extensive study has been carried out on the scope of this direct oxetane fragmentation, and the results have been submitted for publication.
10. K. Nozaki, K. Oshima and K. Utimoto, J. Am. Chem. Soc., 1987, 109, 2547; Tetrahedron Lett., 1988, 29, 6125; 6127.