Enantiospecific Total Synthesis of the Highly Strained (-)-Presilphiperfolan-8-ol via a Pd-Catalyzed Tandem Cyclization
Enantiospecific Total Synthesis of the Highly Strained (-)-Presilphiperfolan-8-ol via a Pd-Catalyzed Tandem Cyclization
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DOI：
10.1021/jacs.7b01454
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发表时间：
2017-04-12
影响因子：
15
通讯作者：
Snyder, Scott A.
中科院分区：
文献类型：
--
作者：
Hu, Pengfei;Snyder, Scott A.
在天然来源的分子中，一种罕见的高应变元素是[3.3.0]-双环内5元环的1，2-融合，这是（-）-presilphiperfolan-8-ol中存在的基序。该分子在其五元环之一上也具有取代基的1，3-反式立体化学排列，这是许多其他萜烯所共有的模式。在此，我们公开了该高度应变的靶的13个步骤的第一全合成。关键操作是Pd催化的串联环化，其直接在一个环上建立必需的1，3-反式立体化学排列，同时为最终结构的高度应变的1，2-反式环融合的受控产生设置阶段。
A rare element of high strain in molecules of natural origin is a 1,2-trans fusion of 5-membered rings within a [3.3.0]-bicycle, a motif present in (-)-presilphiperfolan-8-ol. This molecule also possesses a 1,3-trans stereochemical arrangement of substituents on one of its 5-membered rings, a pattern shared by a number of other terpenes. Herein, we disclose the first total synthesis of this highly strained target in 13 steps. The key operation is a Pd-catalyzed tandem cyclization that directly establishes the requisite 1,3-trans stereochemical arrangement on one ring while concurrently setting the stage for the controlled generation of the highly strained 1,2-trans ring fusion of the final architecture.