Department of Chemistry , University of Munich , Butenandtstraße 5-13 , Munich 81377 , Germany.
Chemistry Research Laboratory , University of Oxford , 12 Mansfield Road , Oxford OX1 3TA , United Kingdom.
J Am Chem Soc. 2018 Jul 18;140(28):8675-8680. doi: 10.1021/jacs.8b01918. Epub 2018 Jul 9.
(+)-Stephadiamine is an unusual alkaloid isolated from the vine Stephania japonica. It features a norhasubanan skeleton, and contains two adjacent α-tertiary amines, which renders it an attractive synthetic target. Here, we present the first total synthesis of stephadiamine, which hinges on an efficient cascade reaction to implement the aza[4.3.3]propellane core of the alkaloid. The α-aminolactone moiety in a highly hindered position was installed via Tollens reaction and Curtius rearrangement. Useful building blocks for the asymmetric synthesis of morphine and (nor)hasubanan alkaloids are introduced.
(+)-Stephadiamine 是从藤本植物Stephania japonica 中分离得到的一种不寻常的生物碱。它具有 norhasubanan 骨架，并且含有两个相邻的α-三级胺，这使其成为一个有吸引力的合成目标。在这里，我们首次全合成了 Stephadiamine，其关键在于通过高效级联反应来实现生物碱的 aza[4.3.3]propellane 核心。通过 Tollens 反应和 Curtius 重排，在高度位阻的位置安装了 α-氨基内酯部分。引入了用于不对称合成吗啡和（nor）hasubanan 生物碱的有用构建块。
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