发展一种对映选择性方法合成石松生物碱：石松堿的全合成。
Development of an enantioselective route toward the Lycopodium alkaloids: total synthesis of lycopodine.
机构信息
Department of Chemistry, Oregon State University, 153 Gilbert Hall, Corvallis, Oregon 97331, USA.
出版信息
J Org Chem. 2010 Aug 6;75(15):4929-38. doi: 10.1021/jo100916x.
Abstract
Synthesis of a C(15)-desmethyl tricycle core of lycopodine has been accomplished. Key steps in the synthetic sequence include organocatalytic, intramolecular Michael addition of a keto sulfone and a tandem 1,3-sulfonyl shift/Mannich cyclization to construct the tricyclic core ring system. Synthetic work toward this natural product family led to the development of N-(p-dodecylphenylsulfonyl)-2-pyrrolidinecarboxamide, an organocatalyst which facilitates enantioselective, intramolecular Michael additions. A detailed mechanistic discussion is provided for both the intramolecular Michael addition and the sulfone rearrangement. Finally, the application of these discoveries to the enantioselective total synthesis of alkaloid lycopodine is described.
摘要
已经完成了石松堿 C(15)-去甲基三环核心的合成。合成序列中的关键步骤包括酮亚砜的有机催化、分子内迈克尔加成以及串联的 1,3-砜基迁移/Mannich 环化，以构建三环核心环系统。针对该天然产物家族的合成工作导致了 N-(对十二烷基苯基磺酰基)-2-吡咯烷甲酰胺的开发，这是一种能够促进对映选择性分子内迈克尔加成的有机催化剂。对分子内迈克尔加成和亚砜重排都提供了详细的机理讨论。最后，描述了这些发现在手性全合成生物碱石松堿中的应用。
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