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Please use this identifier to cite or link to this item: http://hdl.handle.net/10261/51678
Title: Highly Stereoselective Total Synthesis of (+)-9-epi-Dictyostatin and (–)-12,13-bis-epi-Dictyostatin Eur. J
Authors: Zanato, Chiara; Pignataro, Luca; Ambrosi, Andrea; Hao, Zhongyan; Trigili, Chiara; Díaz, José Fernando; Barasoain, Isabel; Gennari, Cesare
Keywords: Medicinal chemistry
Natural products
Total synthesis
Asymmetric synthesis
Antitumor agents
Issue Date: May-2011
Publisher: American Chemical Society
Citation: Journal of Organic Chemistry(14):2643-2661(2011)
Abstract: The total syntheses of (+)-9-epi-dictyostatin (1a) and (–)-12,13-bis-epi-dictyostatin (1b), diastereomers of the antimitotic marine sponge-derived macrolide (–)-dictyostatin (1), were achieved by creating 11 stereogenic centers and 4stereogenic double bonds with a high level of stereocontrol. The yield for the 29-step longest linear sequence from Roche ester was 1.53 and 1.52 %, respectively. The final key steps to these unnatural products were the addition of vinylzincates C10-C26 to aldehyde C1–C9 (leading surprisingly to complete stereoselectivity for the 9R-configuration in 28a and for the 9S-configuration in 12,13-bis-epimeric 28b), followed by Yamaguchi macrolactonization and global deprotection. (–)-12,13-Bis-epi-dictyostatin (1b) displayed a dramatic decrease of cytotoxicity and of the affinity toward the paclitaxel binding site of microtubules
Description: 19 páginas, 9 esquemas, 2 tablas -- PAGS nros. 2643-2661
Publisher version (URL): http:dx.doi.org/10.1002/ejoc.201100244
URI: http://hdl.handle.net/10261/51678
ISSN: 0022-3263
DOI: 10.1002/ejoc.201100244
E-ISSN: 1520-6904
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