Serratezomines A-C, new alkaloids from Lycopodium serratum var. serratum

Journal of Organic Chemistry

Volumn 65, Issue 19, 2000, Pages 6241-6245

  Morita, Hiroshi ^a   Arisaka, Mika ^a   Yoshida, Naotoshi ^a   Kobayashi, Jun'ichi ^a  

^a HOKKAIDO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALKALOID DERIVATIVE; SERRATEZOMINE A; SERRATEZOMINE B; SERRATEZOMINE C; UNCLASSIFIED DRUG;

CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL ANALYSIS; DRUG ISOLATION; DRUG STRUCTURE; MOSS; NONHUMAN; NOTE; NUCLEAR OVERHAUSER EFFECT; PROTON NUCLEAR MAGNETIC RESONANCE; STRUCTURE ANALYSIS;

ALKALOIDS; CIRCULAR DICHROISM; INDOLIZINES; MAGNETIC RESONANCE SPECTROSCOPY; MOSSES; OXIDATION-REDUCTION; SUPPORT, NON-U.S. GOV'T;

EID: 0034703296     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo000661e     Document Type: Note

References (36)

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19. The club moss L. serratum has been used as Chinese traditional medicine, in which the constituent alkaloids, hupderzines A and B, show pronounced anticholinesterase activity and are under clinical investigation in China for the treatment of myasthenia gravis and senile memory loss now recognized as symptoms of Alzheimer's dementia (AD): Liu, J. S.; Zhu, Y. L. Yu, C. M.; Zhou, Y. Z.; Han, Y. Y.; Wu, F. W.; Qi, B. F. Can J. Chem. 1986, 64, 837-839.
20. In the previous study, serratinine (4) and serratanine A have been isolated as major alkaloids from L. serratum var. serratum: (a) Ishii, H.; Yasui, B.; Nishino, R.; Harayama, T.; Inubushi, Y. Chem. Pharm. Bull. 1970, 18, 1880-1888.
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26. a-6 was approximately 90°, resulting in one of the coupling constant being nearly zero.
27. 9 indicated that the indolizidine moiety with cis ring junction was 1.81 kcal/mol lower in energy than that with trans ring junction, although an indolizidine alkaloid, slaframine, has been reported to have trans ring juncture: Pearson, W. H.; Bergmeier, S. C.; Williams, J. P. J. Org. Chem. 1992, 57, 3997-3987.
28. Falk, M.; Spierenburg, P. F.; Walter, J. A. J. Comput. Chem. 1896, 17, 409-417.
29. Interatomic distances were classified into five ranges, ≤ 2.5, ≤3.0, ≤3.5, ≤ 4.0, and ≤5.0 Å, corresponding to the integrated volumes of the 32 NOESY cross-peaks. Interproton distances were calculated from the integrated volumes of the corresponding cross-peaks using the distance between the two H-6 protons as a reference (1.8 Å). Because of the lack of stereospecific assignments in some methylene protons, the upper distances of these methylene and methyl protons were further relaxed by means of the pseudoatoms corrections.
30. This chiral inversion is caused by the application of NOE constraints. When relatively large force constants for the NOE derived distance constraints are used, these constraints become energetically much more important than the torsion and angle energies which are responsible for maintaining the chirality. Once the chirality is inverted simultaneously at both centers, all angles, torsions, and distance constraints are satisfied. This floating chirality technique is much more convenient and goes one step further to increase the level of confidence in the assignment of relative configuration.
31. The absolute stereostructure of serratinine (4) has been established on the basis of the Bijvoet method using X-ray crystal structure of 13-acetyl-8-p-bromobenzoyl derivative of 4: Nishio, K.; Fujiwara, T.; Tomita, K.; Ishii, H.; Inubushi, Y.; Harayama, T. Tetrahedron Lett. 1969, 861-864. In this study, by using direct methods in X-ray analysis, the stereostructure of 4 was confirmed to be the same as that previously reported (see the Supporting Information).
32. R values were negative). Ohtani, I.; Kusumi, T.; Kashman, Y.; Kakisawa, H. J. Am. Chem. Soc. 1991, 113, 4092-4096.
33. Absolute stereostructure of L20 (6) has been established on the basis of chemical correlation with lycopodine (See ref 8). In this study, by X-ray analysis, the stereostructure of 6 was directly confirmed to be the same as that previously reported (see the Supporting Information).
34. Hemscheidt, T.; Spenser, I. D. J. Am. Chem. Soc. 1996, 118, 8, 1799-1800.
35. Inubushi, Y.; Ishii, H.; Yasui, B.; Harayama, T. Tetrahedron Lett. 1966, 1551-1559.
36. Clark, M.; Cramer, R. D., III; Van Opdenbosch, N. J. Comput. Chem. 1989, 10, 982-1012.