Prins成环新策略在天然产物合成中的应用

Under a friendly environmental situation, a TMSI and samarium promoted Prins cyclization has been developed in our group to construct only 2,6-disubstituted tetrahedropyrans. This modified cyclization was employed to the synthesis of (±)-Centrobine, and allowed to achieve a remarkably shorter synthesis. It can also provide the opportunity for a convenient synthesis of natural products, such as (-)-Centrobol, Curcumene ether and Sydowic acid. Extension of this methodology to Prins-Pinacol rearrangement can, if successful, provide a novel approach to THF-based lignans. Furthermore, a novel Prins cyclization cascade reaction will be carried out for the synthesis of quinine ring in one step. It is expected that these procedures are able to provide concise routes for the synthesis of these molecules.

三甲基碘硅烷TMSI和金属钐能够环境友好地构筑仅有2,6位取代的四氢吡喃环，改进后的Prins反应已成功应用于天然产物(±)-Centrobine的合成，相同策略拟合成天然产物(-)-Centrobol，Curcumene ether和Sydowic acid；并基于Prins-Pinacol 重排设计一条合成四氢呋喃型木脂素的通用路线，同时发展新的Prins串联反应来一步构筑奎宁的主要骨架，以期为这些天然产物提供简捷的合成新路线。

我们利用Prins成环反应合成了(-)-centrolobol、(±)-Centrobine和Diosniponol A-B等天然产物，并对木脂素类天然产物和其他二芳基庚烷类化合物进行了合成研究。并基于Prins成环反应对奎宁的合成进行了模型反应，通过串联反应能够构建奎宁环，取得了阶段性进展。此外，我们增加了一些内容，实现了对天然产物Cassumunin C和latifolin的首次合成；对农药啶酰菌胺提供了一条新的合成路线。