Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, Pennsylvania 19104, United States.
Department of Molecular Pharmacology, Albert Einstein College of Medicine, 1300 Morris Park Avenue, Bronx, New York 10461, United States.
J Am Chem Soc. 2021 Feb 3;143(4):1740-1744. doi: 10.1021/jacs.0c11424. Epub 2021 Jan 26.
The enantioselective total syntheses of (+)-peniciketals A and B, two members of a family of architecturally complex spiroketals, have been achieved. Key synthetic transformations comprise Type I Anion Relay Chemistry (ARC) to construct the benzannulated [6,6]-spiroketal skeleton, a Negishi cross-coupling/olefin cross-metathesis reaction sequence to generate the -enone structure, and a late-stage large fragment union exploiting our recently developed photoisomerization/cyclization tactic.
(+)-Peniciketals A 和 B 的对映选择性全合成已经完成，它们是一组具有复杂结构的螺环缩酮家族的成员。关键的合成转化包括 I 型阴离子中继化学（ARC）构建苯并[6,6]-螺环缩酮骨架、Negishi 交叉偶联/烯烃交叉复分解反应序列生成 -烯酮结构，以及利用我们最近开发的光异构化/环化策略进行后期的大片段连接。
