金（I）介导的环化/环加成反应促进了 Neonectrolide B-E 及其类似物的生物灵感合成。
Gold(I)-Mediated Cycloisomerization/Cycloaddition Enables Bioinspired Syntheses of Neonectrolides B-E and Analogues.
机构信息
Department of Chemistry, Center for Molecular Discovery (BU-CMD) , Boston University , 590 Commonwealth Avenue , Boston , Massachusetts 02215 , United States.
出版信息
J Am Chem Soc. 2019 Sep 25;141(38):15135-15144. doi: 10.1021/jacs.9b06355. Epub 2019 Sep 12.
Abstract
Development of a synthetic route to the oxaphenalenone (OP) natural products neonectrolides B-E is described. The synthesis relies on gold-catalyzed 6--dig hydroarylation of an unusual enynol substrate as well as a one-pot Rieche formylation/cyclization/deprotection sequence to efficiently construct the tricyclic oxaphenalenone framework in the form of a masked -quinone methide (-QM). A tandem cycloisomerization/[4 + 2] cycloaddition strategy was employed to quickly construct molecules resembling the neonectrolides. The tricyclic OP natural product SF226 could be converted to corymbiferan lactone E and a related masked QM. Our study culminates with the application of the tandem reaction sequence to syntheses of neonectrolides B-E as well as previously unreported -diastereomers.
摘要
描述了一种合成氧杂蒽酮（OP）天然产物新内脂 B-E 的方法。该合成依赖于金催化的 6--二氢芳基化反应，以及一锅法的 Rieche 甲酰化/环化/脱保护序列，以有效地将三环氧杂蒽酮骨架构建成一种掩蔽的 -醌亚甲基（-QM）形式。采用串联环化/[4 + 2]环加成策略来快速构建类似于新内脂的分子。三环 OP 天然产物 SF226 可以转化为珊瑚烯内酯 E 和相关的掩蔽的-QM。我们的研究最终应用串联反应序列合成了新内脂 B-E 以及以前未报道的 -非对映异构体。
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