The total synthesis of (+)-9-epi-dictyostatin (1b), a diastereomer of the antimitotic marine-sponge-derived macrolide (–)-dictyostatin (1a), was achieved by creating 11 stereogenic centers and 4 stereogenic double bonds with a high level of stereocontrol. The yield for the 29-step longest linear sequence from Roche ester was 1.53%. The final key steps to this unnatural product were the vinylzincate C10–C26 addition to aldehyde C1–C9 (leading surprisingly to a complete stereoselectivity for the 9R-epimer), followed by Yamaguchi macrolactonization and global deprotection.
A Highly Stereoselective Total Synthesis of (+)-9-epi-Dictyostatin / C. Zanato, L. Pignataro, A. Ambrosi, Z. Hao, C. Gennari. - In: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY. - ISSN 1434-193X. - 2010:30(2010 Oct), pp. 5767-5771. [10.1002/ejoc.201001018]
A Highly Stereoselective Total Synthesis of (+)-9-epi-Dictyostatin
C. Zanato;L. Pignataro;C. Gennari
2010
Abstract
The total synthesis of (+)-9-epi-dictyostatin (1b), a diastereomer of the antimitotic marine-sponge-derived macrolide (–)-dictyostatin (1a), was achieved by creating 11 stereogenic centers and 4 stereogenic double bonds with a high level of stereocontrol. The yield for the 29-step longest linear sequence from Roche ester was 1.53%. The final key steps to this unnatural product were the vinylzincate C10–C26 addition to aldehyde C1–C9 (leading surprisingly to a complete stereoselectivity for the 9R-epimer), followed by Yamaguchi macrolactonization and global deprotection.Pubblicazioni consigliate
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