A cyclopropyl group shows reverse facial selectivity depending on the bicyclic ring system

Tetrahedron Letters

Volumn 38, Issue 38, 1997, Pages 6693-6696

  Tsuji, Motonori ^a   Ohwada, Tomohiko ^a   Shudo, Koichi ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

BICYCLO[2.2.2]OCTANE DERIVATIVE; CYCLOPROPANE DERIVATIVE; NORBORNANE DERIVATIVE;

ARTICLE; CHEMICAL STRUCTURE; DRUG CONFORMATION; MOLECULAR STABILITY;

EID: 0030794917     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)01567-0     Document Type: Article

References (36)

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12. Calculated geometries of 5a and 6a, optimized with HF/6-31G* basis sets, show that both compounds exhibit tilting of the olefin plane toward the ethano bridge bearing the cyclopropyl group (data not shown). These geometrical perturbations do not appear to determine the facial selectivity of 5a and 6a, because the reverse facial preference was observed. An X-ray determination of the related aziridine derivative of 7-methylidenenorbornane was previously reported: Maasa, W.; Birkhahn, M.; Landmann, B.; Hoffmann, R.W. Chem. Ber., 1983, 116, 404-408. See also Laube, T., J. Am. Chem. Soc. 1989, 111, 9224-9232.
13. Calculated geometries of 5a and 6a, optimized with HF/6-31G* basis sets, show that both compounds exhibit tilting of the olefin plane toward the ethano bridge bearing the cyclopropyl group (data not shown). These geometrical perturbations do not appear to determine the facial selectivity of 5a and 6a, because the reverse facial preference was observed. An X-ray determination of the related aziridine derivative of 7-methylidenenorbornane was previously reported: Maasa, W.; Birkhahn, M.; Landmann, B.; Hoffmann, R.W. Chem. Ber., 1983, 116, 404-408. See also Laube, T., J. Am. Chem. Soc. 1989, 111, 9224-9232.
14. The configurations of the diol (or epoxide) moieties were elucidated on the basis of the characteristic anisotropy effects of the diols (or the epoxide) and the cyclopropyl group (see c and ). The structures of the some of the major products (syn-diols of 5a and 5c, and syn-epoxide of 5d) were also confirmed by X-ray crystallographic analysis. The structures of the diol of 6a were also elucidated on the basis of the NOE enhancement.
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33. Ohwada T., Uchiyama M., Tsuji M., Okamoto I., Shudo K. Chem. Pharm. Bull. 44:1996;296-306.
34. The energy level of the Walsh orbital (NXHOMO) of cyanocyclopropane is lower than that of unsubstituted cyclopropane. The cyano group also redistributes the orbital coefficients, leading to a reduction of the orbital coefficient of the cyclopropane moiety in the relevant Walsh orbital.
35. A cyclopropyl group showed the divergent anisotropy effect, i.e., deshielding or shielding, depending on the conformation: Christl, M. Chem. Ber., 1975, 108, 2781-2791.; Christl, M.; Herbert, R., Chem. Ber., 1979, 112, 2022-2027. and d. The rigid structures such as 5a and 6a exclude the possible conformational effect of the cyclopropyl group.
36. A cyclopropyl group showed the divergent anisotropy effect, i.e., deshielding or shielding, depending on the conformation: Christl, M. Chem. Ber., 1975, 108, 2781-2791.; Christl, M.; Herbert, R., Chem. Ber., 1979, 112, 2022-2027. and d. The rigid structures such as 5a and 6a exclude the possible conformational effect of the cyclopropyl group.