Enantiospecific first total synthesis and assignment of absolute configuration of the sesquiterpene (-)-cucumin H

Organic Letters

Volumn 5, Issue 13, 2003, Pages 2295-2298

  Srikrishna, A ^a   Dethe, Dattatraya H ^a  

^a INDIAN INSTITUTE OF SCIENCE   (India)

Author keywords

[No Author keywords available]

Indexed keywords

LIMONENE; NATURAL PRODUCT; SESQUITERPENE DERIVATIVE;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; DRUG ISOLATION; DRUG STRUCTURE; DRUG SYNTHESIS; ENANTIOSELECTIVITY; INFRARED SPECTROSCOPY; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY; X RAY DIFFRACTION;

CRYSTALLOGRAPHY, X-RAY; CYCLOPENTANES; MOLECULAR CONFORMATION; NITROBENZOATES; OXIDATION-REDUCTION; SESQUITERPENES; STEREOISOMERISM; TERPENES;

EID: 0141518529     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol034635p     Document Type: Article

References (27)

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5. Isolation of ceratopicanol: Hanssen, H.-P.; Abraham, W.-R. Tetrahedron 1988, 44, 2175. For synthesis, see: Mehta, G.; Karra, S. R. J. Chem. Soc., Chem. Commun. 1991, 1367. Clive, D. L. J.; Magnuson, S. R. Tetrahedron Lett. 1995, 36, 15. Baralotto, C.; Chanon, M.; Julliard, M. J. Org. Chem. 1996, 61, 3576. Paquette, L. A.; Geng, F. J. Am. Chem. Soc. 2002, 124, 9199. Anger, T.; Graalmann, O.; Schroder, H.; Gerke, R.; Kaiser, U.; Fitjer, L.; Noltemeyer, M. Tetrahedron 1998, 54, 10713. Mukai, C.; Kobayashi, M.; Kim, I. J.; Hanaoka, M. Tetrahedron 2002, 58, 5225.
6. Isolation of ceratopicanol: Hanssen, H.-P.; Abraham, W.-R. Tetrahedron 1988, 44, 2175. For synthesis, see: Mehta, G.; Karra, S. R. J. Chem. Soc., Chem. Commun. 1991, 1367. Clive, D. L. J.; Magnuson, S. R. Tetrahedron Lett. 1995, 36, 15. Baralotto, C.; Chanon, M.; Julliard, M. J. Org. Chem. 1996, 61, 3576. Paquette, L. A.; Geng, F. J. Am. Chem. Soc. 2002, 124, 9199. Anger, T.; Graalmann, O.; Schroder, H.; Gerke, R.; Kaiser, U.; Fitjer, L.; Noltemeyer, M. Tetrahedron 1998, 54, 10713. Mukai, C.; Kobayashi, M.; Kim, I. J.; Hanaoka, M. Tetrahedron 2002, 58, 5225.
7. Isolation of ceratopicanol: Hanssen, H.-P.; Abraham, W.-R. Tetrahedron 1988, 44, 2175. For synthesis, see: Mehta, G.; Karra, S. R. J. Chem. Soc., Chem. Commun. 1991, 1367. Clive, D. L. J.; Magnuson, S. R. Tetrahedron Lett. 1995, 36, 15. Baralotto, C.; Chanon, M.; Julliard, M. J. Org. Chem. 1996, 61, 3576. Paquette, L. A.; Geng, F. J. Am. Chem. Soc. 2002, 124, 9199. Anger, T.; Graalmann, O.; Schroder, H.; Gerke, R.; Kaiser, U.; Fitjer, L.; Noltemeyer, M. Tetrahedron 1998, 54, 10713. Mukai, C.; Kobayashi, M.; Kim, I. J.; Hanaoka, M. Tetrahedron 2002, 58, 5225.
8. Isolation of ceratopicanol: Hanssen, H.-P.; Abraham, W.-R. Tetrahedron 1988, 44, 2175. For synthesis, see: Mehta, G.; Karra, S. R. J. Chem. Soc., Chem. Commun. 1991, 1367. Clive, D. L. J.; Magnuson, S. R. Tetrahedron Lett. 1995, 36, 15. Baralotto, C.; Chanon, M.; Julliard, M. J. Org. Chem. 1996, 61, 3576. Paquette, L. A.; Geng, F. J. Am. Chem. Soc. 2002, 124, 9199. Anger, T.; Graalmann, O.; Schroder, H.; Gerke, R.; Kaiser, U.; Fitjer, L.; Noltemeyer, M. Tetrahedron 1998, 54, 10713. Mukai, C.; Kobayashi, M.; Kim, I. J.; Hanaoka, M. Tetrahedron 2002, 58, 5225.
9. Isolation of ceratopicanol: Hanssen, H.-P.; Abraham, W.-R. Tetrahedron 1988, 44, 2175. For synthesis, see: Mehta, G.; Karra, S. R. J. Chem. Soc., Chem. Commun. 1991, 1367. Clive, D. L. J.; Magnuson, S. R. Tetrahedron Lett. 1995, 36, 15. Baralotto, C.; Chanon, M.; Julliard, M. J. Org. Chem. 1996, 61, 3576. Paquette, L. A.; Geng, F. J. Am. Chem. Soc. 2002, 124, 9199. Anger, T.; Graalmann, O.; Schroder, H.; Gerke, R.; Kaiser, U.; Fitjer, L.; Noltemeyer, M. Tetrahedron 1998, 54, 10713. Mukai, C.; Kobayashi, M.; Kim, I. J.; Hanaoka, M. Tetrahedron 2002, 58, 5225.
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18. In addition, a small amount (< 5%) of the corresponding bis-thioketal (easily separable) was also formed.
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21. 3).
22. The structure of alcohol 23 was further confirmed by the single-crystal X-ray diffraction analysis of the p-nitrobenzoate ester of alcohol 23 (CCDC deposition number CCDC 201351)
23. Kent, G. J.; Wallis, E. S. J. Org. Chem. 1959, 24, 1235.
24. A reduction-protection-allylic oxidation-deprotection protocol was also explored for the regiocontrolled conversion of the enone 25 into cucumin H, but was unsuccessful.
25. Hughes, D. L. Org. React. 1992, 42, 335.
26. o) and 0.0875 for all 7649 data. wR2 = 0.1228, GOF = 0.878. There are three independent molecules in the asymmetric unit. An ORTEP drawing of compound 28 with a 50% ellipsoidal probability level is shown in Figure 1 (only one molecule is shown and hydrogen atoms are removed for clarity). Crystallographic data are being deposited with the Cambridge Crystallographic Data Center (CCDC 201351)
27. Theoretical calculations (MNDO and AM1 level) indicated that exo sides of both the C 3 and C 7 ketones in 26 are equally preferred for the hydride attack, which is followed by the endo face of the C 3 ketone, whereas the endo face of the C 7 ketone is hindered for the hydride attack. However, the origin of the total difference in regioselectivity between the sodium borohydride-cerium chloride and lithium aluminum hydride in the reduction of 26 is not clear.