Synthesis of the C2-symmetric, macrocyclic alkaloid, (+)-xestospongin A and its C(9)-epimer, (-)-xestospongin C: Impact of substrate rigidity and reaction conditions on the efficiency of the macrocyclic dimerization reaction

Journal of the American Chemical Society

Volumn 118, Issue 48, 1996, Pages 12074-12081

  Hoye, Thomas R ^a   Ye, Zhixiong ^a   Yao, Letitia J ^a   North, Jeffrey T ^a  

^a University of Minnesota ^*  (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKALOID; MACROCYCLIC COMPOUND; UNCLASSIFIED DRUG; XESTOSPONGIN A; XESTOSPONGIN C;

ARTICLE; CHIRALITY; DRUG SYNTHESIS; ENANTIOMER; NUCLEAR MAGNETIC RESONANCE; PH; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030458293     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja962671w     Document Type: Article

References (19)

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15. 8c However, the procedures for preparing 20-27 are included as Supporting Information for this paper since improvements in yield accompanied scale-up in work done subsequent to the preliminary report.
16. ent-Xestospongin A (-)-1 was also prepared by the stepwise route proceeding from (-)-27 via ent-28-Ac, ent-29, ent-trans-30-Ac, ent-cis-30-Ac, ent-31, and (+)-32 [where -Ac designates the acetate ester of the enantiomers of the corresponding alcohols 28, trans-30, and cis-30 (Scheme 5)].
17. (a) β-Hydroxynitriles: Itoh, T.; Takagi, Y.; Nishiyama, S. J. Org. Chem. 1991, 56, 1521. (b) SP-435: Johnson, C. R.; Bis, S. J. Tetrahedron Lett. 1992, 33, 7287.
18. (a) β-Hydroxynitriles: Itoh, T.; Takagi, Y.; Nishiyama, S. J. Org. Chem. 1991, 56, 1521. (b) SP-435: Johnson, C. R.; Bis, S. J. Tetrahedron Lett. 1992, 33, 7287.
19. (a) Under acidic conditions, (-)-32 decomposed slowly (2 days) at room temperature and extensively at 80°C (1 day). (b) We judge that as little as 5% of the stereoisomer would have been detectable given the open spectral windows in the chemical shift ranges where we could confidently anticipate resonances for the diastereomer to appear.