Access to the Akuammiline Family of Alkaloids: Total Synthesis of (+)-Scholarisine A

The planning and implementation of an enantioselective
total synthesis of (+)-scholarisine A is presented. Key tactics employed
include a novel cyclization, consisting of a nitrile reduction coupled
with concomitant addition of the resultant amine to an epoxide; a
modified Fischer indolization; an oxidative lactonization of a diol
in the presence of an indole ring; and a late-stage cyclization to
complete the caged ring scaffold. The development of a possible “retro-biosynthetic”
approach to other members of the akuammiline alkaloid family is also
described.

本文报道了(+)-帽柱木碱A [(+)-scholarisine A]的对映选择性全合成的规划与实施。所采用的关键合成策略包括：一种新型环化反应——即腈基还原与生成的胺同步进攻环氧基团的串联反应；一种改良的费歇尔吲哚合成反应（Fischer indolization）；在吲哚环存在下完成二醇的氧化内酯化反应；以及用于构筑笼状环骨架的后期环化步骤。此外，本文还介绍了一种可用于合成阿枯米灵生物碱家族（akuammiline alkaloid family）其他成员的“逆生物合成（retro-biosynthetic）”潜在路径。