کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1345450 | 980201 | 2015 | 6 صفحه PDF | دانلود رایگان |
A short and efficient enantioselective synthesis of marine macrolide stagonolide E in high enantiomeric purity (98% ee and 8.5% overall yield) starting from commercially available raw materials has been achieved. The strategy involves proline catalyzed sequential α-aminooxylation and Horner–Wadsworth–Emmons olefination, highly stereoselective Ando’s cis-olefination, and modified Yamaguchi macrolactonization as the key reaction steps.
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(S)-6-(Benzyloxy)-hexane-1,2-diolC13H20O3ee 98% determined by chiral HPLC[α]D25 = −3.2 (c 1.0, CHCl3)Source of chirality: d-proline catalyzed α-aminooxylationAbsolute configuration: (S)
Ethyl-(4R,7R,E)-7-((tert-butyldimethylsilyl)oxy)-4-hydroxyoct-2-enoateC16H20O4Side 98% determined by chiral HPLC[α]D25 = −13.1 (c 1.8, CHCl3)Source of chirality: l-proline catalyzed α-aminooxylation followed by HWE olefinationAbsolute configuration: (4R,7R,E)
Ethyl-(3Z,5E,7R,10R)-10-((tert-butyldimethylsilyl)oxy)-7-(methoxymethoxy)-2-oxoundeca-3,5-dienoateC21H38O6Si[α]D25 = +81.2 (c 1.2, CHCl3)Source of chirality: l-proline catalyzed α-aminooxylation followed by HWE olefinationAbsolute configuration: (3Z,5E,7R,10R)
Ethyl-(3Z,5E,7R,10R)-10-hydroxy-7-(methoxymethoxy)-2-oxoundeca-3,5-dienoateC15H24O6[α]D25 = +68.0 (c 0.4, CHCl3)Source of chirality: l-proline catalyzed α-aminooxylation followed by HWE olefinationAbsolute configuration: (3Z,5E,7R,10R)
(3Z,5E,7R,10R)-10-Hydroxy-7-(methoxymethoxy)-2-oxoundeca-3,5-dienoic acidC13H20O6[α]D25 = +37.6 (c 1, CHCl3)Source of chirality: l-proline catalyzed α-aminooxylation followed by HWE olefinationAbsolute configuration: (3Z,5E,7R,10R)
Journal: Tetrahedron: Asymmetry - Volume 26, Issue 7, 15 April 2015, Pages 344–349