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

我们开发了一种通过加热SiliaBond^[○！R]苯基（硅胶，其表面上具有苯基基团）与Hg（0Ac）_2在AcOH中使用微波辐射加热至140 ° C，然后用TfOH处理。该固载三氟甲磺酸汞催化剂对吲哚合成、呋喃炔环化、芳炔环化、串联碳环化和烯丙基胺化等反应均表现出良好的催化活性。因为SiliaBond^[○！[R] Phenyl是一种用于柱色谱的硅胶，我们通过简单地将固定化催化剂装入小玻璃管中，建立了一种用于吲哚合成和芳基炔环化的高效流动反应系统。此外，使用固体催化剂的高金合欢酸的催化串联碳环化用于（±）-菌体蛋白的全合成，并进行类似物以允许详细检查菌体蛋白的faliaceous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.