Chi Hyung Min, Cole Charles J F, Hu Pengfei, Taylor Cooper A, Snyder Scott A
Department of Chemistry, University of Chicago 5735 S. Ellis Avenue Chicago IL 60637 USA
Chem Sci. 2020 Sep 30;11(40):10939-10944. doi: 10.1039/d0sc04686h.
The recent natural product isolates spiroviolene and spirograterpene A are two relatively non-functionalized linear triquinane terpenes with a large number of structural homologies. Nevertheless, three significant areas of structural disparity exist based on their original assignments, one of which implies a key stereochemical divergence early in their respective biosyntheses. Herein, using two known bicyclic ketone intermediates, a core Pd-catalyzed Heck cyclization sequence, and several chemoselective transformations, we describe concise total syntheses of both natural product targets and propose that the structure of spiroviolene should be reassigned. As a result, these natural products possess greater homology than previously anticipated.
最近分离得到的天然产物螺旋紫罗兰烯和螺旋大香叶烯A是两种相对未官能化的线性三环萜烯，它们具有大量的结构同源性。然而，根据它们最初的归属，存在三个显著的结构差异区域，其中一个暗示了在它们各自生物合成早期的关键立体化学分歧。在此，我们利用两种已知的双环酮中间体、一个核心的钯催化Heck环化序列以及几种化学选择性转化反应，描述了这两种天然产物目标分子的简洁全合成，并提出螺旋紫罗兰烯的结构应重新归属。结果，这些天然产物具有比先前预期更大的同源性。
