Total synthesis of (+)-dysidiolide

Journal of Organic Chemistry

Volumn 63, Issue 2, 1998, Pages 228-229

  Boukouvalas, John ^a   Cheng, Yun Xing ^a   Robichaud, Joël ^a  

^a UNIVERSITÉ LAVAL   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

ANTINEOPLASTIC AGENT; DYSIDIOLIDE; UNCLASSIFIED DRUG;

ANTINEOPLASTIC ACTIVITY; ARTICLE; CHIRALITY; DRUG CONFORMATION; DRUG ISOLATION; DRUG SYNTHESIS; ENZYME INHIBITION; SPONGE (PORIFERA); STEREOCHEMISTRY; STRUCTURE ACTIVITY RELATION;

EID: 0032559199     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo972208h     Document Type: Article

References (25)

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3. Structural elucidation by NMR was particularly difficult due to the presence of both lactol epimers in solution and/or the hindered motions of the lactol ring (ref 1).
4. Boukouvalas, J.; Lachance. N. Synlett 1998, in press.
5. Molecular mechanics calculations using CHARMm forcefield quanta simulation software indicated that this conformer corresponds to the lowest energy minimum and is favored by at least 1.1 kcal/mol over those susceptible to undergo si-face attack. We thank Professor Josée Brisson for invaluable assistance.
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13. 3 was essential for optimal results; see also: Ladouceur, G.; Paquette, L. A. Synthesis 1992, 185. Dimitrov, V.; Kostova, K.; Genov, M. Tetrahedron Lett. 1996, 37, 6787.
14. Yields refer to chromatographically and spectroscopically homogeneous products. All new compounds exhibited satisfactory elemental analyses and/or exact mass data.
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19. The structural assignments to these diols follow from NOE studies. Details of these experiments will be provided in the full paper.
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21. Ireland, R. E.; Muchmore, D. C.; Hengartner, U. J. Am. Chem. Soc. 1972, 94, 5098. See also: Trost, B. M.; Renaut, P. J. Am. Chem. Soc. 1982, 104, 6668. Wender, P. A.; von Geldern, T. W.; Levine, B. H. J. Am. Chem. Soc. 1988, 110, 4858.
22. Ireland, R. E.; Muchmore, D. C.; Hengartner, U. J. Am. Chem. Soc. 1972, 94, 5098. See also: Trost, B. M.; Renaut, P. J. Am. Chem. Soc. 1982, 104, 6668. Wender, P. A.; von Geldern, T. W.; Levine, B. H. J. Am. Chem. Soc. 1988, 110, 4858.
23. 3, -78 to +25 °C) using Eberbach's procedure (Haarmann, H.; Eberbach, W. Tetrahedron Lett. 1991, 32, 903).
24. Alcohols 20 and 21 were produced in excellent yield (>90%) and a ratio of 2.2:1, as determined by HPLC analysis of the crude reaction mixture. The relatively low yield of the minor isomer 21 after chromatography, which was less polar than 20, was due to partial coelution with the 2-[(triisopropylsilyl)oxy]furan byproduct arising by hydrolysis of unreacted 19.
25. We are grateful to Dr. Sarath Gunasekera of Harbor Branch Oceanographic Institution for a sample of natural dysidiolide.