Key Laboratory of Green Chemistry & Technology of the Ministry of Education, College of Chemistry, Sichuan University, Chengdu, Sichuan 610064, China.
J Am Chem Soc. 2013 Jun 26;135(25):9291-4. doi: 10.1021/ja4040335. Epub 2013 Jun 11.
We report the first total synthesis of bolivanine in a 14-step pathway involving the synthesis of onoseriolide. Our synthesis features a palladium-catalyzed intramolecular cyclopropanation involving an allylic metal carbene and a Diels-Alder/intramolecular hetero-Diels-Alder cascade, allowing the single-step assembly of a tricyclic system with proper configuration. The synthetic efforts validate our modified biogenetic hypothesis and allow us to confirm the absolute configuration of bolivianine.
我们报告了在涉及奥诺塞里醇内酯合成的 14 步途径中首次全合成博利文碱。我们的合成特征在于钯催化的涉及烯丙基金属卡宾和 Diels-Alder/内型杂 Diels-Alder 级联的分子内环丙烷化，允许通过一步组装具有适当构型的三环系统。这些合成工作验证了我们修改后的生物发生假说，并使我们能够确认博利文碱的绝对构型。
