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Total Synthesis of ( ‒ )-Colombiasin A and ( ‒ )-Elisapterosin B by two different approaches

Total Synthesis of ( ‒ )-Colombiasin A and ( ‒ )-Elisapterosin B by two different approaches. A presentation by Guillaume Pelletier April 27 th 2012. Structural and biological analysis.

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Total Synthesis of ( ‒ )-Colombiasin A and ( ‒ )-Elisapterosin B by two different approaches

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  1. Total Synthesis of (‒)-Colombiasin A and (‒)-Elisapterosin B by two different approaches A presentation by Guillaume Pelletier April 27th 2012

  2. Structural and biological analysis • These molecules are additions to the family of diterpenes from the gorgonian octacoral Pseudopterogorgia elisabethae (isolated by Rodriguez et al. in early 2000) • Possess potential antiplasmodial activity against plasmodium falciparum, the parasite responsible for the most severe forms of malaria and is an in vitro inhibitor of Mycobacterium tuberculosis H37Rb • Total synthesis by many groups : Harrowven (2005, ■and■), Nicolaou (2001, ■), Rychnovsky (2003, ■and■), Rawal (2003, ■), Davies (2006, ■), Jacobsen and Boezio, A. A. (2005, ■ and■) Nicolaou, K. C.; Edmonds, D. J.; Bulger, P. G. Angew. Chem., Int. Ed. 2006, 45, 7134-7186.

  3. Various approaches to the targets Harrowvenm D. C.; Pascoe, D. D.; Demurtas, D.; Bourne, H. O. Angew. Chem., Int. Ed. 2005, 44, 1221-1222. Waizumi, N.; Stankovic, A. R.; Rawal, V. R. J. Am. Chem. Soc. 2003, 125, 13022-13023.

  4. Harrowven’s approach to (‒)-Colombiaisin A Harrowvenm D. C.; Pascoe, D. D.; Demurtas, D.; Bourne, H. O. Angew. Chem., Int. Ed. 2005, 44, 1221-1222.

  5. Harrowven’s approach to (‒)-Colombiaisin A Harrowvenm D. C.; Pascoe, D. D.; Demurtas, D.; Bourne, H. O. Angew. Chem., Int. Ed. 2005, 44, 1221-1222.

  6. Harrowven’s approach to (‒)-Colombiaisin A Brown, H. C.; Singaram, B. Acc. Chem. Res. 1988, 21, 287-298. Brown, H. C.; Ramachandran, P. V. J. Organomet. Chem. 1995, 500, 1-19. Matteson, D. S. Synthesis 1996, 973-985.

  7. Harrowven’s approach to (‒)-Colombiaisin A Brown, H. C.; Singaram, B. Acc. Chem. Res. 1988, 21, 287-298. Brown, H. C.; Ramachandran, P. V. J. Organomet. Chem. 1995, 500, 1-19. Matteson, D. S. Synthesis 1996, 973-985.

  8. Harrowven’s approach to (‒)-Colombiaisin A Harrowvenm D. C.; Pascoe, D. D.; Demurtas, D.; Bourne, H. O. Angew. Chem., Int. Ed. 2005, 44, 1221-1222.

  9. Harrowven’s approach to (‒)-Colombiaisin A Harrowvenm D. C.; Pascoe, D. D.; Demurtas, D.; Bourne, H. O. Angew. Chem., Int. Ed. 2005, 44, 1221-1222.

  10. Kocienski’s modification of Julia olefination (BT sulfone) Baudin, J. B.; Hareau, G.; Julia, S. H.; Lorne, R.; Ruel, O. Bull. Chim. Soc. Fr. 1993, 130, 856-878. Smith, N. D.; Kocienski, P. J.; Street, D. A. S. Synthesis1996, 652-666.

  11. Kocienski’s modification of Julia olefination (BT sulfone) Cyclic (Chelate) TS favoured for non-polar solvent, small counter-ions (Li) Open TS favoured for polar solvents, large counter-ions (K) Baudin, J. B.; Hareau, G.; Julia, S. H.; Lorne, R.; Ruel, O. Bull. Chim. Soc. Fr. 1993, 130, 856-878. Smith, N. D.; Kocienski, P. J.; Street, D. A. S. Synthesis1996, 652-666.

  12. Kocienski’s modification of Julia olefination (BT sulfone) Cyclic (Chelate) TS favoured for non-polar solvent, small counter-ions (Li) Open TS favoured for polar solvents, large counter-ions (K) Charette, A. B.; Lebel, H. J. Am. Chem. Soc. 1996, 118, 10327-10328.

  13. Harrowven’s approach to (‒)-Colombiaisin A Harrowvenm D. C.; Pascoe, D. D.; Demurtas, D.; Bourne, H. O. Angew. Chem., Int. Ed. 2005, 44, 1221-1222.

  14. Modified Bamford-Stevens (Shapiro) olefination Harrowvenm D. C.; Pascoe, D. D.; Demurtas, D.; Bourne, H. O. Angew. Chem., Int. Ed. 2005, 44, 1221-1222. Reed, M. W.; Pollart, D. J.; Perri, S. T.; Foland, L. D.; Moore, H. W. J. Org. Chem. 1988, 53, 2477 – 2482. Shapiro, R. H. Org. React. 1976, 26, 405-507.

  15. Bamford-Stevens olefination in protic and aprotic solvents Casanova, J.; Waegell, B. Bull. Chim. Soc. Fr. 1975, 922-932. Nickon, A.; Bronfenbrenner, J. K. J. Am. Chem. Soc. 1982, 104, 2022-2023.

  16. Harrowven’s approach to (‒)-Colombiaisin A Harrowvenm D. C.; Pascoe, D. D.; Demurtas, D.; Bourne, H. O. Angew. Chem., Int. Ed. 2005, 44, 1221-1222.

  17. Moore rearrangement of vinylcyclobutene to hydroquinone Harrowvenm D. C.; Pascoe, D. D.; Demurtas, D.; Bourne, H. O. Angew. Chem., Int. Ed. 2005, 44, 1221-1222. Karlsson, J. O.; Nguyen, N. V.; Foland, L. D.; Moore, H. W. J. Am. Chem. Soc. 1985, 107, 3392-3393. Perri, S. T.; Dyke, H. J.; Moore, H.W. J. Org. Chem. 1989, 54, 2032-2034.

  18. Harrowven’s approach to (‒)-Colombiaisin A To be continued… Harrowvenm D. C.; Pascoe, D. D.; Demurtas, D.; Bourne, H. O. Angew. Chem., Int. Ed. 2005, 44, 1221-1222.

  19. Rawal’s approach to (‒)-Elisapterosin B Waizumi, N.; Stankovic, A. R.; Rawal, V. R. J. Am. Chem. Soc. 2003, 125, 13022-13023.

  20. Diazotization with HNO2 Carey, F. A.; Sundberg, R. J. in “Advanced Organic Chemistry”, Springer, ed.; 4th Edition, Chap.

  21. Rawal’s approach to (‒)-Elisapterosin B Waizumi, N.; Stankovic, A. R.; Rawal, V. R. J. Am. Chem. Soc. 2003, 125, 13022-13023. Negishi, E.; Bagheri, V.; Chatterjee, S.; Luo, F. T.; Miller, J. A.; Stoll, A. T. Tetrahedron Lett. 1983,24, 5181-5184.

  22. Rawal’s approach to (‒)-Elisapterosin B Waizumi, N.; Stankovic, A. R.; Rawal, V. R. J. Am. Chem. Soc. 2003, 125, 13022-13023. Negishi, E.; Bagheri, V.; Chatterjee, S.; Luo, F. T.; Miller, J. A.; Stoll, A. T. Tetrahedron Lett. 1983,24, 5181-5184.

  23. Rawal’s approach to (‒)-Elisapterosin B Waizumi, N.; Stankovic, A. R.; Rawal, V. R. J. Am. Chem. Soc. 2003, 125, 13022-13023.

  24. Seyfert-Gilbert alkynylation Waizumi, N.; Stankovic, A. R.; Rawal, V. R. J. Am. Chem. Soc. 2003, 125, 13022-13023. Seyferth, D.; Marmor, R. S.; Hilbert, P. J. Org. Chem. 1971, 36, 1379-1386. Colvin, E. W.; Hamill, B. J. J. Chem. Soc., Chem. Commun.1973, 151-152. Gilbert, J. C.; Weerasooriya, U. J. Org. Chem. 1979, 44, 4997-4998.

  25. Rawal’s approach to (‒)-Elisapterosin B Waizumi, N.; Stankovic, A. R.; Rawal, V. R. J. Am. Chem. Soc. 2003, 125, 13022-13023.

  26. Pinacol-type rearrangment of ketal Tsuchihashi, G., Kitajima, K., Mitamura, M. Tetrahedron Lett. 1981, 22, 4305-4308. Honda, Y.; Ori, A.; Tsuchihashi, G. Bull. Chem. Soc. Jpn. 1987, 60, 1027-1036.

  27. Rawal’s approach to (‒)-Elisapterosin B Waizumi, N.; Stankovic, A. R.; Rawal, V. R. J. Am. Chem. Soc. 2003, 125, 13022-13023.

  28. Rawal’s approach to (‒)-Elisapterosin B Waizumi, N.; Stankovic, A. R.; Rawal, V. R. J. Am. Chem. Soc. 2003, 125, 13022-13023.

  29. Rawal’s approach to (‒)-Elisapterosin B Waizumi, N.; Stankovic, A. R.; Rawal, V. R. J. Am. Chem. Soc. 2003, 125, 13022-13023.

  30. Salcomine catalyzed aerobic oxidation of phenol Van Dort, H. M.; Geursen, H. J. Recl. Trav. Chim. Pays-Bas 1967, 86, 520-526. Parker, K. A.; Petraitis, J. J. Tetrahedron Lett. 1981, 22, 397-400.

  31. Rawal’s approach to (‒)-Elisapterosin B Waizumi, N.; Stankovic, A. R.; Rawal, V. R. J. Am. Chem. Soc. 2003, 125, 13022-13023.

  32. Endo-selective Diels-Alder Waizumi, N.; Stankovic, A. R.; Rawal, V. R. J. Am. Chem. Soc. 2003, 125, 13022-13023.

  33. Rawal’s approach to (‒)-Elisapterosin B Waizumi, N.; Stankovic, A. R.; Rawal, V. R. J. Am. Chem. Soc. 2003, 125, 13022-13023.

  34. CAN mediated oxidative cyclisation Waizumi, N.; Stankovic, A. R.; Rawal, V. R. J. Am. Chem. Soc. 2003, 125, 13022-13023. Zanoni, G.;Franzini, M. Angew. Chem., Int. Ed. 2004, 43, 4837-4841.

  35. (‒)-Colombiaisin A to (‒)-Elisapterosin B with BF3•OEt2 Boezio, A. A.; Jarvo, E. R.; Lawrence, B. M.; Jacobsen, E. N. Angew. Chem., Int. Ed. 2005, 44, 6046-6050.

  36. (‒)-Colombiaisin A to (‒)-Elisapterosin B with BF3•OEt2 Boezio, A. A.; Jarvo, E. R.; Lawrence, B. M.; Jacobsen, E. N. Angew. Chem., Int. Ed. 2005, 44, 6046-6050. Nicolaou, K. C.; Edmonds, D. J.; Bulger, P. G. Angew. Chem., Int. Ed. 2006, 45, 7134-7186.

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