Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States.
J Am Chem Soc. 2022 Apr 13;144(14):6193-6199. doi: 10.1021/jacs.2c02144. Epub 2022 Apr 4.
A new polyene cyclization strategy exploiting β-ionyl derivatives was developed. Photoinduced deconjugation of the extended π-system within these chromophores unveils a contrathermodynamic polyene that engages in a Heck bicyclization to afford [4.4.1]-propellanes. This cascade improves upon the limited regioselectivity achieved using existing biomimetic tactics and tolerates both electron-rich and electron-deficient (hetero)aryl groups. The utility of this approach was demonstrated with the diverted total synthesis of taxodione and salviasperanol, two isomeric abietane diterpenes that were previously inaccessible along the same synthetic pathway.
开发了一种利用β-异戊烯基衍生物的新聚烯环化策略。这些生色团中扩展的π体系的光诱导去共轭，揭示了一个逆热力学聚烯，它参与 Heck 双环化反应，生成[4.4.1]-丙二烯。该级联反应提高了使用现有仿生策略获得的有限区域选择性，并耐受富电子和缺电子（杂）芳基。该方法的实用性通过 taxodione 和 salviasperanol 的定向全合成得到了证明，这两种异戊二烯二萜是以前在同一合成途径中无法获得的。
