Design of Solid Supported Metal Catalyst and The Application to Synthesis of Thallusin Analogues

我们开发了一种方法，通过加热硅氧烷来生成第一个固体负载汞盐，硅苯汞三酸盐。[4]苯基（表面有苯基的硅胶）与Hg(OAc)_2在AcOH中经TfOH处理后，微波辐射至140℃。该固体负载型三氟化汞对吲哚合成、呋喃烷环化、芳炔环化、串联碳环化和烯丙基胺化具有显著的催化活性。因为sililiabond ^[〇！]苯基是一种用于柱层析的硅胶，我们通过在一个小玻璃管中简单地充电固定催化剂，建立了一个高效的流动反应体系，用于吲哚合成和芳炔环化。此外，利用固体催化剂对同型香草酸进行串联碳环化催化合成了（±）-菌藻素，并进行了类似物的研究，以详细检查菌藻素的虚假形态诱导活性。

We developed a procedure to generate the first solid supported mercuric salt, silaphenylmercuric triflate, by heating SiliaBond^[○!R] Phenyl (silica gel with phenyl group on its surface) with Hg(OAc)_2 in AcOH to 140℃ using microwave radiation following treatment with TfOH. This solid supported mercuric triflate showed remarkable catalytic activity for a indole synthesis, furanoyne cyclization, arylyne cyclization, tandem carbocyclization, and allylic amination. Because the SiliaBond^[○!R] Phenyl is a silica gel used for column chromatography, we established a highly efficient flow-reaction system useful for indole synthesis and arylyne cyclization by simply charging the immobilized catalyst in a small glass tube. Moreover, catalytic tandem carbocyclization of homofarnesic acid using the solid catalyst was utilized for the total synthesis of (±)-thallusin and analogues were undertaken to allow a detailed examination of thallusin's faliaceous morphology-inducing activity.