First access to enantiopure C(7)-substituted fenchones: New norbornane-based chiral materials from the chiral pool

Tetrahedron Asymmetry

Volumn 14, Issue 12, 2003, Pages 1607-1609

  García Martínez, Antonio ^a   Teso Vilar, Enrique ^b   García Fraile, Amelia ^b   De La Moya Cerero, Santiago ^a   Lora Maroto, Beatriz ^b  

^a UNIVERSIDAD COMPLUTENSE DE MADRID   (Spain)

^b UNIVERSIDAD NACIONAL DE EDUCACIÓN A DISTANCIA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

1,3,3 TRIMETHYL 2 NORCAMPHANONE; CHEMICAL COMPOUND; NORBORNANE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHIRALITY; MODEL; PRIORITY JOURNAL; STEREOCHEMISTRY;

EID: 0037867717     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0957-4166(03)00307-0     Document Type: Article

References (26)

1. As a general review, see: (a) Oppolzer, W. Tetrahedron 1987, 43, 1969; (b) Money, T. Nat. Prod. Rep. 1985, 2, 253; (c) Ho, T.-L. In Enantioselective Synthesis: Natural Products from Chiral Terpenes; John Wiley and Sons: New York, 1992; (d) Money, T. In Studies in Natural Products Chemistry; Atta-ur-Rahmann, Ed.; Elsevier: Amsterdam, 1989; (e) Eliel, E. L.; Wilen, S. H. In Stereochemistry of Organic Compounds; John Wiley and Sons: New York, 1994; (f) Seyden-Penne J. In Chiral Auxiliaries and Ligands in Asymmetric Synthesis; John Wiley and Sons: New York, 1995.
2. As a general review, see: (a) Oppolzer, W. Tetrahedron 1987, 43, 1969; (b) Money, T. Nat. Prod. Rep. 1985, 2, 253; (c) Ho, T.-L. In Enantioselective Synthesis: Natural Products from Chiral Terpenes; John Wiley and Sons: New York, 1992; (d) Money, T. In Studies in Natural Products Chemistry; Atta-ur-Rahmann, Ed.; Elsevier: Amsterdam, 1989; (e) Eliel, E. L.; Wilen, S. H. In Stereochemistry of Organic Compounds; John Wiley and Sons: New York, 1994; (f) Seyden-Penne J. In Chiral Auxiliaries and Ligands in Asymmetric Synthesis; John Wiley and Sons: New York, 1995.
3. As a general review, see: (a) Oppolzer, W. Tetrahedron 1987, 43, 1969; (b) Money, T. Nat. Prod. Rep. 1985, 2, 253; (c) Ho, T.-L. In Enantioselective Synthesis: Natural Products from Chiral Terpenes; John Wiley and Sons: New York, 1992; (d) Money, T. In Studies in Natural Products Chemistry; Atta-ur-Rahmann, Ed.; Elsevier: Amsterdam, 1989; (e) Eliel, E. L.; Wilen, S. H. In Stereochemistry of Organic Compounds; John Wiley and Sons: New York, 1994; (f) Seyden-Penne J. In Chiral Auxiliaries and Ligands in Asymmetric Synthesis; John Wiley and Sons: New York, 1995.
4. As a general review, see: (a) Oppolzer, W. Tetrahedron 1987, 43, 1969; (b) Money, T. Nat. Prod. Rep. 1985, 2, 253; (c) Ho, T.-L. In Enantioselective Synthesis: Natural Products from Chiral Terpenes; John Wiley and Sons: New York, 1992; (d) Money, T. In Studies in Natural Products Chemistry; Atta-ur-Rahmann, Ed.; Elsevier: Amsterdam, 1989; (e) Eliel, E. L.; Wilen, S. H. In Stereochemistry of Organic Compounds; John Wiley and Sons: New York, 1994; (f) Seyden-Penne J. In Chiral Auxiliaries and Ligands in Asymmetric Synthesis; John Wiley and Sons: New York, 1995.
5. As a general review, see: (a) Oppolzer, W. Tetrahedron 1987, 43, 1969; (b) Money, T. Nat. Prod. Rep. 1985, 2, 253; (c) Ho, T.-L. In Enantioselective Synthesis: Natural Products from Chiral Terpenes; John Wiley and Sons: New York, 1992; (d) Money, T. In Studies in Natural Products Chemistry; Atta-ur-Rahmann, Ed.; Elsevier: Amsterdam, 1989; (e) Eliel, E. L.; Wilen, S. H. In Stereochemistry of Organic Compounds; John Wiley and Sons: New York, 1994; (f) Seyden-Penne J. In Chiral Auxiliaries and Ligands in Asymmetric Synthesis; John Wiley and Sons: New York, 1995.
6. As a general review, see: (a) Oppolzer, W. Tetrahedron 1987, 43, 1969; (b) Money, T. Nat. Prod. Rep. 1985, 2, 253; (c) Ho, T.-L. In Enantioselective Synthesis: Natural Products from Chiral Terpenes; John Wiley and Sons: New York, 1992; (d) Money, T. In Studies in Natural Products Chemistry; Atta-ur-Rahmann, Ed.; Elsevier: Amsterdam, 1989; (e) Eliel, E. L.; Wilen, S. H. In Stereochemistry of Organic Compounds; John Wiley and Sons: New York, 1994; (f) Seyden-Penne J. In Chiral Auxiliaries and Ligands in Asymmetric Synthesis; John Wiley and Sons: New York, 1995.
7. As a general overview on the functionalization see Ref. 1b. On the functionalization of the C(10)-position see Ref. 6.
8. For 3, see: (a) Helmchen, G.; Goeke, A.; Lauer, G.; Ulmann, M.; Fries, J. Angew. Chem., Int. Ed. Engl. 1990, 29, 9; (b) Kramp, P.; Helmchen, G.; Holmes, A. B. J. Chem. Soc., Chem. Commun. 1993, 551; (c) Clive, D. L. J.; Ou, L. Tetrahedron Lett. 2002, 43, 4559. For 4, see: (d) Metha, G.; Mohal, N. Tetrahedron Lett. 1999, 40, 5791; (e) Metha, G.; Mohal, N. Tetrahedron Lett. 1999, 40, 5795; (f) Metha, G.; Mohal, N. Tetrahedron Lett. 2001, 42, 4227. For 5, see: (g) Levitt, M. S.; Newton, R. G.; Roberts, S. M.; Willetts, A. J. J. Chem. Soc., Chem. Commun. 1990, 8, 619. For 6, see: (h) Naemura, K.; Takahashi, N.; Tanaka, S.; Ida; H. J. Chem. Soc., Perkin Trans. 1 1992, 2337 and references cited therein.
9. For 3, see: (a) Helmchen, G.; Goeke, A.; Lauer, G.; Ulmann, M.; Fries, J. Angew. Chem., Int. Ed. Engl. 1990, 29, 9; (b) Kramp, P.; Helmchen, G.; Holmes, A. B. J. Chem. Soc., Chem. Commun. 1993, 551; (c) Clive, D. L. J.; Ou, L. Tetrahedron Lett. 2002, 43, 4559. For 4, see: (d) Metha, G.; Mohal, N. Tetrahedron Lett. 1999, 40, 5791; (e) Metha, G.; Mohal, N. Tetrahedron Lett. 1999, 40, 5795; (f) Metha, G.; Mohal, N. Tetrahedron Lett. 2001, 42, 4227. For 5, see: (g) Levitt, M. S.; Newton, R. G.; Roberts, S. M.; Willetts, A. J. J. Chem. Soc., Chem. Commun. 1990, 8, 619. For 6, see: (h) Naemura, K.; Takahashi, N.; Tanaka, S.; Ida; H. J. Chem. Soc., Perkin Trans. 1 1992, 2337 and references cited therein.
10. For 3, see: (a) Helmchen, G.; Goeke, A.; Lauer, G.; Ulmann, M.; Fries, J. Angew. Chem., Int. Ed. Engl. 1990, 29, 9; (b) Kramp, P.; Helmchen, G.; Holmes, A. B. J. Chem. Soc., Chem. Commun. 1993, 551; (c) Clive, D. L. J.; Ou, L. Tetrahedron Lett. 2002, 43, 4559. For 4, see: (d) Metha, G.; Mohal, N. Tetrahedron Lett. 1999, 40, 5791; (e) Metha, G.; Mohal, N. Tetrahedron Lett. 1999, 40, 5795; (f) Metha, G.; Mohal, N. Tetrahedron Lett. 2001, 42, 4227. For 5, see: (g) Levitt, M. S.; Newton, R. G.; Roberts, S. M.; Willetts, A. J. J. Chem. Soc., Chem. Commun. 1990, 8, 619. For 6, see: (h) Naemura, K.; Takahashi, N.; Tanaka, S.; Ida; H. J. Chem. Soc., Perkin Trans. 1 1992, 2337 and references cited therein.
11. For 3, see: (a) Helmchen, G.; Goeke, A.; Lauer, G.; Ulmann, M.; Fries, J. Angew. Chem., Int. Ed. Engl. 1990, 29, 9; (b) Kramp, P.; Helmchen, G.; Holmes, A. B. J. Chem. Soc., Chem. Commun. 1993, 551; (c) Clive, D. L. J.; Ou, L. Tetrahedron Lett. 2002, 43, 4559. For 4, see: (d) Metha, G.; Mohal, N. Tetrahedron Lett. 1999, 40, 5791; (e) Metha, G.; Mohal, N. Tetrahedron Lett. 1999, 40, 5795; (f) Metha, G.; Mohal, N. Tetrahedron Lett. 2001, 42, 4227. For 5, see: (g) Levitt, M. S.; Newton, R. G.; Roberts, S. M.; Willetts, A. J. J. Chem. Soc., Chem. Commun. 1990, 8, 619. For 6, see: (h) Naemura, K.; Takahashi, N.; Tanaka, S.; Ida; H. J. Chem. Soc., Perkin Trans. 1 1992, 2337 and references cited therein.
12. For 3, see: (a) Helmchen, G.; Goeke, A.; Lauer, G.; Ulmann, M.; Fries, J. Angew. Chem., Int. Ed. Engl. 1990, 29, 9; (b) Kramp, P.; Helmchen, G.; Holmes, A. B. J. Chem. Soc., Chem. Commun. 1993, 551; (c) Clive, D. L. J.; Ou, L. Tetrahedron Lett. 2002, 43, 4559. For 4, see: (d) Metha, G.; Mohal, N. Tetrahedron Lett. 1999, 40, 5791; (e) Metha, G.; Mohal, N. Tetrahedron Lett. 1999, 40, 5795; (f) Metha, G.; Mohal, N. Tetrahedron Lett. 2001, 42, 4227. For 5, see: (g) Levitt, M. S.; Newton, R. G.; Roberts, S. M.; Willetts, A. J. J. Chem. Soc., Chem. Commun. 1990, 8, 619. For 6, see: (h) Naemura, K.; Takahashi, N.; Tanaka, S.; Ida; H. J. Chem. Soc., Perkin Trans. 1 1992, 2337 and references cited therein.
13. For 3, see: (a) Helmchen, G.; Goeke, A.; Lauer, G.; Ulmann, M.; Fries, J. Angew. Chem., Int. Ed. Engl. 1990, 29, 9; (b) Kramp, P.; Helmchen, G.; Holmes, A. B. J. Chem. Soc., Chem. Commun. 1993, 551; (c) Clive, D. L. J.; Ou, L. Tetrahedron Lett. 2002, 43, 4559. For 4, see: (d) Metha, G.; Mohal, N. Tetrahedron Lett. 1999, 40, 5791; (e) Metha, G.; Mohal, N. Tetrahedron Lett. 1999, 40, 5795; (f) Metha, G.; Mohal, N. Tetrahedron Lett. 2001, 42, 4227. For 5, see: (g) Levitt, M. S.; Newton, R. G.; Roberts, S. M.; Willetts, A. J. J. Chem. Soc., Chem. Commun. 1990, 8, 619. For 6, see: (h) Naemura, K.; Takahashi, N.; Tanaka, S.; Ida; H. J. Chem. Soc., Perkin Trans. 1 1992, 2337 and references cited therein.
14. For 3, see: (a) Helmchen, G.; Goeke, A.; Lauer, G.; Ulmann, M.; Fries, J. Angew. Chem., Int. Ed. Engl. 1990, 29, 9; (b) Kramp, P.; Helmchen, G.; Holmes, A. B. J. Chem. Soc., Chem. Commun. 1993, 551; (c) Clive, D. L. J.; Ou, L. Tetrahedron Lett. 2002, 43, 4559. For 4, see: (d) Metha, G.; Mohal, N. Tetrahedron Lett. 1999, 40, 5791; (e) Metha, G.; Mohal, N. Tetrahedron Lett. 1999, 40, 5795; (f) Metha, G.; Mohal, N. Tetrahedron Lett. 2001, 42, 4227. For 5, see: (g) Levitt, M. S.; Newton, R. G.; Roberts, S. M.; Willetts, A. J. J. Chem. Soc., Chem. Commun. 1990, 8, 619. For 6, see: (h) Naemura, K.; Takahashi, N.; Tanaka, S.; Ida; H. J. Chem. Soc., Perkin Trans. 1 1992, 2337 and references cited therein.
15. For 3, see: (a) Helmchen, G.; Goeke, A.; Lauer, G.; Ulmann, M.; Fries, J. Angew. Chem., Int. Ed. Engl. 1990, 29, 9; (b) Kramp, P.; Helmchen, G.; Holmes, A. B. J. Chem. Soc., Chem. Commun. 1993, 551; (c) Clive, D. L. J.; Ou, L. Tetrahedron Lett. 2002, 43, 4559. For 4, see: (d) Metha, G.; Mohal, N. Tetrahedron Lett. 1999, 40, 5791; (e) Metha, G.; Mohal, N. Tetrahedron Lett. 1999, 40, 5795; (f) Metha, G.; Mohal, N. Tetrahedron Lett. 2001, 42, 4227. For 5, see: (g) Levitt, M. S.; Newton, R. G.; Roberts, S. M.; Willetts, A. J. J. Chem. Soc., Chem. Commun. 1990, 8, 619. For 6, see: (h) Naemura, K.; Takahashi, N.; Tanaka, S.; Ida; H. J. Chem. Soc., Perkin Trans. 1 1992, 2337 and references cited therein.
16. For an example, see kinetic resolution of racemic 5 in Ref. 3g.
17. Lumb J.T., Whitham G.H. Chem. Commun. 1966;400.
18. Nash J.J., Waugh T., Morrison H. Tetrahedron Lett. 39:1998;6449.
19. Jenkins M.N., Nash J.J., Morrison H. Tetrahedron Lett. 43:2002;3773.
20. de la Moya Cerero S., García Martínez A., Teso Vilar E., García Fraile A., Lora Maroto B. J. Org. Chem. 68:2003;1451. and references cited therein.
21. Since the starting commercial (-)-fenchone 2 has an ee of 82% all products enantiospecifically obtained from it must possess the same enantiomeric excess. This fact has been previously tested by us (García Martínez, A., Teso Vilar, E.; García Fraile, A.; de la Moya Cerero, S.; Lora Maroto, B. Tetrahedron: Asymmetry 2001, 12, 3325).
22. 13C NMR and HRMS agree with the structure.
23. On the enantiospecific reaction of (-)-fenchone with triflic anhydride see Ref. 6. Elution-chromatography separation yields minority triflate 8 in 12% yield as a colorless oil.
24. Silica gel/hexane.
25. 13C NMR and HRMS agree with the structures. The stereochemistry was confirmed by NOE experiments.
26. About a related tandem proton addition-Wagner-Meerwein rearrangement, see Ref. 6.