Total Synthesis, Structure Revision, and Absolute Configuration of (+)-Yatakemycin

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• 作者：Mark S. Tichenor ; David B. Kastrinsky ; and Dale L. Boger
• 刊名：Journal of the American Chemical Society
• 出版年：2004
• 出版时间：July 14, 2004
• 年：2004
• 卷：126
• 期：27
• 页码：8396 - 8398
• 全文大小：117K
• 年卷期：v.126,no.27(July 14, 2004)
• ISSN：1520-5126

文摘

The total synthesis of the reported structure 2 for yatakemycin, an exceptionally potent, naturally occurring antitumor agent disclosed in 2003, and its lack of correlation with the natural product are detailed. On the basis of spectroscopic distinctions between 2 and yatakemycin, the natural product structure was reformulated as 3, now bearing a thiomethyl ester versus thioacetate in the left-hand subunit. Total synthesis of 3 provided a compound nearly identical to but still subtly distinct from the natural product. A second reformulation of the yatakemycin structure as 1, incorporating the alternatively substituted right-hand subunit as well as the initial thiomethyl ester reformulation, was confirmed by total synthesis of both (+)- and ent-(-)-1 in studies that also unambiguously established the absolute configuration of the natural product.