手性氨基酸三唑金(Ⅲ)催化剂的设计合成及其在不对称催化中的应用

Biological medicines, pesticide, dyes and other fine chemicals most contain heterocyclic or chiral heterocyclic structure. Asymmetric catalysis is an effective method to build these chiral heterocyclic compounds with high efficiency and high selectivity. Among this, the stability of gold catalyst system plays a decisive role. This project will design and synthsize new types of amino acid triazole gold(III) catalysts from commercial available as starting materials, which provides an effective methods to overcome the limitations of gold catalysis. With these gold(III) catalysts in hand, the project will focus on the following research areas: gold-catalyzed asymmetric hydroalkoxylation reaction, hydroamination reaction; gold-catalyzed desymmetrization reaction of diyne compounds and 1,2 rearrangement reaction; The key problem is: stability of gold(III) catalysts; AgX induced accelerated decomposition of gold(III) catalysts. The synthesis of high coordination and free phosphine ligand could improve the stability of gold (III) catalysts. It could avoid the accelerated decomposition gold(III) catalysts due to without introduction of silver reagent in catalytic reactions. The preliminary results show that this project is feasible.

生物医药、农药、染料和其它精细化工品大部分都含有手性杂环结构，而不对称金催化是实现高效、高选择性构建手性杂环化合物的有效方法。其中，金催化体系稳定与否起着决定性的作用。本项目拟从简单原料出发，设计合成新型骨架的氨基酸三唑(吲唑)配体，以获得稳定性较高的手性金(III)催化体系。并将手性金(III)催化体系应用于：金催化联烯的不对称氢烷氧化反应、不对称氢胺化反应；金催化二炔醇衍生物的去对称化反应和金催化的1,2迁移重排反应。关键问题是：金催化剂的稳定性；絮状沉淀AgX引起的金催化剂加速分解。拟解决方案：合成无膦、配位能力较强的双齿或三齿三唑(吲唑)配体提高金(III)稳定性；催化反应中不使用银试剂避免金(III)的加速分解。目前初步的研究结果表明这一课题是可行的。

金催化是有机化学的热点领域之一，其中，新型配体的设计合成是实现高效、高选择性金催化的关键。本项目从简单原料出发，设计合成新型骨架配体的金催化剂，重点研究：1）金催化联烯的合成反应及其尝试氢胺化反应；2）金催化水解反应，3，3 迁移重排反应；3）金催化的醇酮的烷基化反应及其醌的转化衍生化反应；4）金催化的机理研究。该项目的实施为快速发展金催化提供了一定的理论指导和实验依据，并且对发展新的方法学、构建具有潜在应用价值的功能化分子具有重要意义。