Total Synthesis of (+)-Amphidinolide A. Structure Elucidation and Completion of the Synthesis

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• 作者：Barry M. Trost ; Paul E. Harrington ; John D. Chisholm ; and Stephen T. Wrobleski
• 刊名：Journal of the American Chemical Society
• 出版年：2005
• 出版时间：October 5, 2005
• 年：2005
• 卷：127
• 期：39
• 页码：13598 - 13610
• 全文大小：377K
• 年卷期：v.127,no.39(October 5, 2005)
• ISSN：1520-5126

文摘

The structure elucidation of (+)-amphidinolide A, a cytotoxic macrolide, has been accomplishedby employing a combination of NMR chemical shift analysis and total synthesis. The 20-membered ring ofamphidinolide A was formed by a ruthenium-catalyzed alkene-alkyne coupling to forge the C15-C16bond. Using the reported structure 1 as a starting point, a number of diastereomers of amphidinolide Awere prepared. Deviations of the chemical shift of key protons in each isomer relative to the natural materialwere used as a guide to determine the locations of the errors in the relative stereochemistry. Thespectroscopic data for the synthetic and natural material are in excellent agreement.