Reeder Matthew D, Srikanth G S C, Jones Spencer B, Castle Steven L
Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84602, USA.
Org Lett. 2005 Mar 17;7(6):1089-92. doi: 10.1021/ol050020b.
[reaction: see text] The tricyclic core of the bioactive natural product acutumine has been synthesized. Key steps include an oxidative phenolic coupling to form a masked o-benzoquinone, an anionic oxy-Cope rearrangement to construct an all-carbon quaternary center, and a Michael-type cyclization to form an amine-bearing quaternary carbon. The target compound exists in solution as an enol, in contrast to related compounds that are ketones. A model explaining these observations is presented.
[反应：见正文] 生物活性天然产物尖刺碱的三环核心已被合成。关键步骤包括氧化酚偶联以形成掩蔽的邻苯醌，阴离子氧-Cope重排以构建全碳季碳中心，以及迈克尔型环化以形成含胺季碳。与相关的酮类化合物不同，目标化合物在溶液中以烯醇形式存在。本文提出了一个解释这些观察结果的模型。
