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DOI: 10.1039/A606081A (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 1, 1997, 1209-1214

New asymmetric route to bridged indole alkaloids: formal enantiospecific syntheses of (-)-suaveoline, (-)-raumacline and (-)-N[hair space]b-methylraumacline

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Patrick D. Bailey, Ian D. Collier, Sean P. Hollinshead, Madeleine H. Moore, Keith M. Morgan, David I. Smith and John M. Vernon

Abstract

The homologous nitrile 13 derived from L-tryptophan undergoes a modified Pictet–Spengler reaction with methyl propynoate, under conditions of kinetic control, to afford the cis-tetrahydro-β-carboline 15a (cis∶trans = 77∶23). After protection, Dieckmann–Thorpe cyclisation to the bridged keto nitrile 20 proceeds in 90% yield. Simple functional group modifications via the alcohol 21a and nitrile 22 (structures confirmed by X-ray crystallography) allow convergence with the tetracyclic α,β-unsaturated aldehyde 10, which is an advanced intermediate for the synthesis of a range of bridged indole alkaloids.

References

  1. Milestone syntheses of ajmaline include the first total synthesis (S. Masamune, S. K. Ang, C. Egli, N. Nakatsuka, S. Sarkar and Y. Yasunari, J. Am. Chem. Soc., 1967, 89, 2506) and a biomimetic approach (E. E. van Tamelen and L. K. Oliver, J. Am. Chem. Soc., 1970, 92, 2136) Search PubMed.
  2. (a) M. L. Trudell, D. Soerens, R. W. Weber, L. Hutchins, D. Grubisha, D. Bennett and J. M. Cook, Tetrahedron, 1992, 10, 1805 CrossRef CAS; (b) X. Fu and J. M. Cook, J. Am. Chem. Soc., 1992, 114, 6910 CrossRef CAS; (c) L. Zhang, Y. Bi, F. Yu, G. Menzia and J. M. Cook, Heterocycles, 1992, 34, 517 CAS; (d) X. Fu and J. M. Cook, J. Org. Chem., 1993, 58, 661 CrossRef CAS.
  3. For example, P. Magnus, B. Mugrage, M. R. DeLuca and G. A. Cain, J. Am. Chem. Soc., 1990, 112, 5520 Search PubMed.
  4. P. D. Bailey and N. R. McLay, J. Chem. Soc., Perkin Trans. 1, 1993, 441 RSC.
  5. J. Vercauteren, C. Lavaud, J. Levy and G. Massiot, J. Org. Chem., 1984, 49, 2278 CrossRef CAS.
  6. P. D. Bailey and S. P. Hollinshead, J. Chem. Soc., Perkin Trans. 1, 1988, 739 RSC.
  7. Preliminary communication— P. D. Bailey, I. D. Collier, S. P. Hollinshead, M. H. Moore, K. M. Morgan, D. I. Smith and J. M. Vernon, J. Chem. Soc., Chem. Commun., 1994, 1559 Search PubMed.
  8. J. P. Kutney, G. K. Eigendorf, H. Matsue, A. Murai, K. Tanaka, W. L. Sung, K. Wada and B. R. Worth, J. Am. Chem. Soc., 1978, 100, 938 CrossRef CAS.
  9. P. D. Bailey and S. P. Hollinshead, Tetrahedron Lett., 1987, 28, 2879 CrossRef CAS.
  10. P. D. Bailey, S. P. Hollinshead, M. H. Moore, K. M. Morgan, D. I. Smith and J. M. Vernon, Tetrahedron Lett., 1994, 35, 3585 CrossRef CAS.
  11. J. A. Dale, D. L. Dull and H. F. Mosher, J. Org. Chem., 1969, 34, 2543 CrossRef CAS.
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