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Recent Developments and Applications in Enantioselective Desymmetrisation

Recent Developments and Applications in Enantioselective Desymmetrisation. Xin Linghu Department of Chemistry University of North Carolina, Chapel Hill. Outline. Introduction Enantioselective Desymmetrisation of Different Functional Groups Cyclic anhydrides Epoxides

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Recent Developments and Applications in Enantioselective Desymmetrisation

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  1. Recent Developments and Applications in Enantioselective Desymmetrisation Xin Linghu Department of Chemistry University of North Carolina, Chapel Hill

  2. Outline • Introduction • Enantioselective Desymmetrisation of Different Functional Groups • Cyclic anhydrides • Epoxides • Aldehydes and Ketones • Alkenes • Diols • Summary • Acknowledgement

  3. Introduction to Enantioselective Desymmetrisation

  4. Enantioselective Desymmetrisation in Total Synthesis 1987, Schreiber: 1992, Harada:

  5. Enantioselective Desymmetrisation of Cyclic Anhydride: Previous Work 1985, Oda: configuration 1999, Bolm: 1995, Seebach:

  6. Formation of C-X Bond via Anhydrides Chen, Y.; Tian, S.-K.; Deng, L. J. Am. Chem. Soc. 2000, 122, 9542-9543.

  7. Formation of C-C Bond via Anhydrides Bercot, E. A.; Rovis, T. J. Am. Chem. Soc. 2002, 124, 174-175.

  8. Formation of C-C Bond via Anhydrides Shintani, R.; Fu, G. C. Angew. Chem. Int. Ed. 2002, 41, 1057-1059.

  9. Formation of C-C Bond via Anhydrides Shintani, R.; Fu, G. C. Angew. Chem. Int. Ed. 2002, 41, 1057-1059.

  10. Enantioselective Desymmetrisation of Epoxides: Previous Work

  11. Enantioselective Desymmetrisation of Epoxides: Previous Work Cat. (10 mol), 4A MS

  12. Enantioselective Ring Opening Catalyzed by Planar-Chiral Pyridine N-Oxides Tao, B.; Lo, M. M. C.; Fu, G. C. J. Am. Chem. Soc. 2001, 123, 353-354.

  13. Enantioselective Ring Opening Catalyzed by Chiral Bipyridine N,N’-Dioxide Derivatives Nakajima, M.; Saito, M.; Uemura, M.; Hashimoto, S. Tetrahedron Lett.2002, 43, 8827-8829.

  14. Asymmetric Ring Opening with TMSCN Catalyzed by (pybox)Yb Complexes Schaus, S. E.; Jacobsen, E. N. Org. Lett.2000, 2, 1001-1004.

  15. Enantioselective Alkylation of Vinyloxiranes Bertozzi, F.; Crotti, P.; Macchia, F.; Pineschi, M.; Arnold, A.; Feringa, B. L. Org. Lett.2000, 2, 933-936.

  16. Desymmetrisation by Enantioselective Deprotonation Hodgson, D. M.; Gibbs, A. R.; Lee, G. P. Tetrahedron1996, 52, 14361-14384.

  17. Enantioselective a-Deprotonation of Epoxides: Previous Work 1996, Hodgson: 1996, Hodgson:

  18. Enantioselective b-Deprotonation of Epoxides: Previous Work 1980, Whitesell and Felman: 1993, Milne and Murphy: 1998, Andersson:

  19. Enantioselective Alkylative Double Ring Opening of Epoxides Hodgson, D. M.; Maxwell, C. R.; Miles, T. J.; Paruch, E.; Stent, M. A. H.; Matthews, I. R.; Wilson, F. X.; Witherington, J. Angew. Chem. Int. Ed. 2002, 41, 4313-4316.

  20. Enantioselective Alkylative Double Ring Opening of Epoxides Hodgson, D. M.; Maxwell, C. R.; Miles, T. J.; Paruch, E.; Stent, M. A. H.; Matthews, I. R.; Wilson, F. X.; Witherington, J. Angew. Chem. Int. Ed. 2002, 41, 4313-4316.

  21. a-Deprotonated Epoxides as Nucleophiles Hodgson, D. M.; Gras, E. Angew. Chem. Int. Ed. 2002, 41, 2376-2378.

  22. First Desymmetrisation of Centrosymmetric Diepoxide in Natural Product Synthesis Holland, J. M.; Lewis, M.; Nelson, A. Angew. Chem. Int. Ed. 2001, 40, 4082-4084.

  23. First Desymmetrisation of Centrosymmetric Diepoxide in Natural Product Synthesis Holland, J. M.; Lewis, M.; Nelson, A. Angew. Chem. Int. Ed. 2001, 40, 4082-4084.

  24. Enantioselective Desymmetrisation of Ketones and Aldehydes: Previous Work 1984, Hanessian: 1998, Arai and Shioiri: 1990, Roush: 1998, Takemoto:

  25. Enantioselective Desymmetrisation of Ketones and Aldehydes: Previous Work 1998, Ward: 1995, Aubé: 1997, Bolm:

  26. Enantioselective Baeyer-Villiger Oxidations by Transition Metal Catalysis Uchida, T.; Katsuki, T.; Ito, K.; Akashi, S.; Ishii, A.; Kuroda, T. Helv. Chim. Acta 2002, 85, 3078-3089. Watanabe, A.; Uchida, T.; Ito, K.; Katsuki, T. Tetrahedron Lett. 2002, 43, 4481-4485.

  27. Enantioselective Baeyer-Villiger Oxidations by Organocatalysis Murahashi, S.-I.; Ono, S.; Imada, Y. Angew. Chem. Int. Ed. 2002, 41, 2366-2368.

  28. Rhodium-Catalyzed Desymmetrisation of 4-Alkynals Tanaka, K.; Fu, G. C. J. Am. Chem. Soc. 2002, 124, 10296-10297.

  29. Enantioselective Reduction of 2-Alkyl-1,3-diketones Ohtsuka, Y.; Koyasu, K.; Ikeno, T.; Yamada, T. Org. Lett.2001, 3, 2543-2546.

  30. Synthesis of a Potential Intermediate for Pseudomonic Acid B Honda, T.; Kimura, N. Org. Lett.2002, 4, 4567-4570.

  31. Enantioselective Desymmetrisation of Alkenes: Previous Work 1987, Schreiber: 1996, Landais: 1990, Ito:

  32. Enantioselective Desymmetrisation of Alkenes: Previous Work 1985, Whitesell: 1992, Mikami: 1994, Martin:

  33. Enantioselective Desymmetrisation of Alkenes: Previous Work 1998, Schrock and Hoveyda:

  34. Preparation of Cyclic Amines Through Mo-Catalyzed Asymmetric RCM Dolman, S. J.; Sattely, E. S.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 2002, 124, 6991-6997.

  35. Enantioselective Ru-Catalyzed RCM Seiders, T. J.; Ward, D. W.; Grubbs, R. H. Org. Lett.2001, 3, 3225-3228.

  36. Enantioselective Ru-Catalyzed RCM Seiders, T. J.; Ward, D. W.; Grubbs, R. H. Org. Lett.2001, 3, 3225-3228.

  37. Tandem Catalytic Asymmetric ROM/RCM Weatherhead, G. S.; Ford, J. G.; Alexanian, E. J.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc.2000, 122, 1828-1829.

  38. Tandem Catalytic Asymmetric ROM/RCM Weatherhead, G. S.; Ford, J. G.; Alexanian, E. J.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc.2000, 122, 1828-1829.

  39. Desymmetrisation of Meso Bicyclic Hydrazines by Enantioselective Hydroboration Luna, A. P.; Ceschi, M. A.; Bonin, M.; Micouin, L.; Husson, H. P.; Gougeon, S.; Estenne-Bouhtou, G.; Marabout, B.; Sevrin, M.; George, P. J. Org. Chem. 2002, 67, 3522-3524.

  40. Desymmetrisation of Meso Bicyclic Hydrazines by Enantioselective Hydroboration Luna, A. P.; Ceschi, M. A.; Bonin, M.; Micouin, L.; Husson, H. P.; Gougeon, S.; Estenne-Bouhtou, G.; Marabout, B.; Sevrin, M.; George, P. J. Org. Chem. 2002, 67, 3522-3524.

  41. Asymmetric Synthesis of Polyhydroxylated Celastraceae Sesquiterpene Cores Spivey, A. C.; Woodhead, S. J.; Weston, M.; Andrews, B. I. Angew. Chem. Int. Ed. 2001, 40, 769-771.

  42. Enantioselective Desymmetrisation of Meso-Decalin Diallylic Alcohols by Zr-Based SAE Spivey, A. C.; Woodhead, S. J.; Weston, M.; Andrews, B. I. Angew. Chem. Int. Ed. 2001, 40, 769-771.

  43. Enantioselective Desymmetrisation of Diols: Previous Work 1998, Oriyama: 1998, Fu: 1996, Trost:

  44. Enantioselective Desymmetrisation of Diols: Previous Work 1997, Fujioka: 1997, Harada:

  45. Pd-Catalyzed Enantioselective Oxidation Jensen, D. R.; Pugsley, J. S.; Sigman, M. S. J. Am. Chem. Soc. 2001, 123, 7475-7476.

  46. Asymmetric Oxidation of Meso-Diols under Photo-Irradiation Shimizu, H.; Nakata, K.; Katsuki, T. Chem. Lett.2002, 1080-1081.

  47. Enantioselective Desymmetrisation of Meso Cyclic Allylic Bisdiethylphosphate Piarulli, U.; Daubos, P.; Claverie, C; Roux, M; Gennari, C. Angew. Chem. Int. Ed. 2003, 42, 234-236.

  48. Pd-Catalyzed Enantioselective Ring Opening with Dialkylzinc Lautens, M.; Renaud, J.-L.; Hiebert, S. J. Am. Chem. Soc. 2000, 122, 1804-1805.

  49. Rh-Catalyzed Enantioselective Ring Opening with Organoboronic Acids Lautens, M.; Dockendorff, C.; Fagnou, K.; Malicki, A. Org. Lett.2002, 4, 1311-1314.

  50. Desymmetrisation of Diols with a Dinuclear Zinc Asymmetric Catalyst Trost, B. M.; Mino, T. J. Am. Chem. Soc. ASAP

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