Enantioselective synthesis of the cyclopentyl core of the axinellamines [9]

Journal of the American Chemical Society

Volumn 122, Issue 36, 2000, Pages 8793-8794

  Starr, Jeremy T ^a   Koch, Guido ^a   Carreira, Erick M ^a  

^a NONE

Author keywords

[No Author keywords available]

Indexed keywords

AXINELLAMINE DERIVATIVE; GUANIDINE DERIVATIVE; UNCLASSIFIED DRUG;

ANTIBACTERIAL ACTIVITY; CHEMICAL STRUCTURE; ENANTIOMER; LETTER; RACEMIC MIXTURE; STEREOCHEMISTRY; SYNTHESIS; X RAY CRYSTALLOGRAPHY;

EID: 0034644391     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0019575     Document Type: Letter

References (24)

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8. 1H NMR analysis.
9. (a) Sawamura, M.; Kawaguchi, Y.; Nakamura, E. Synlett 1997, 801.
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13. Analytically pure samples could be readily obtained by crystallization from cyclohexane.
14. Bolm, C.; Gerlach, A.; Dinter, C. L. Synlett 1999, 195.
15. 1H NMR spectrum.
16. The structure of 16 was determined by X-ray diffraction analysis, confirming the stereochemical outcome of cyclopropyl carbinyl radical fragmentation (11 → 12), methanolysis (14 → 15), and Cα-epimerization (15 → 16).
17. 2Pyr as a ligand for osmium imparted minimal diastereoselectivity, its use was necessary for achieving the desired chemoselectivity in the dihydroxylation step.
18. Schroder, M. Chem. Rev. 1980, 80, 187 and references therein.
19. (a) AM1 minimization of simplified models of 21 and 22 on PC-Spartan Pro indicated a 3.1 kcal/mol preference for the trans-dialdehyde.
20. 3 in a similar epimerization see: Hibbs, D. E.; Hursthouse, M. B.; Jones, I. G.; Jones, W.; Malik, K. M. A.; North, M. J. Org. Chem. 1999, 64, 5413.
21. Barton, D. H. R.; Crich, D.; Motherwell, W. B. Tetrahedron 1985, 41, 3901.
22. The selectivity for 23 in the acetal-forming reaction was established by reciprocal NOE enhancements between the acetal methine proton and the carbamate N-H proton as well as the aldehyde α-proton and the carbamate N-H in the mono aldehyde 23. AM1 calculations indicate that there is only a minor energy difference (0.3 kcal/mol) between the heats of formation of the two possible acetals. We speculate that the reaction is under kinetic control by factors that are unclear presently. Studies are underway to provide insight into the observed group selectivity.
23. Abiko, A.; Roberts, J. C.; Takewasa, T.; Masamune, S. Tetrahedron Lett. 1986, 27, 4537.
24. 1H NMR.