新型手性非血红素模拟酶及其分子氧活化的不对称催化作用

The asymmetric catalytic oxidation reaction induced by mimic chiral non-heme enzyme catalyst exhibits more and more obvious advantages in the preparation of optical pure oxygen-containing compounds under high efficiency, high selectivity and mild conditions. At present, the asymmetric catalytic oxidation reaction induced by mimic chiral non-heme enzyme catalyst with hydrogen peroxide as an oxidant has made great progress. However, the asymmetric catalytic oxidation reaction induced by the chiral non-heme enzyme catalyst with more green molecular oxygen as the oxidant is still lagging behind. This project focuses on chiral modification of several highly effective non-heme enzyme model complexes reported in the present literature and to explore the asymmetric catalytic oxidation reaction via molecular oxygen activation under biomimetic synergistic substrates or alone. We hope our studies will lay a certain foundation for the asymmetric catalytic oxidation reaction of the non-heme enzyme chiral catalyst with molecular oxygen as the oxidant.

模拟手性非血红素酶催化剂引发的不对称催化氧化反应在高效高选择性温和条件下制备光学纯含氧化合物方面具有越来越明显的优势。目前，以双氧水为氧化剂，模拟手性非血红素酶催化剂引发的不对称催化氧化反应已取得长足的进展，然而以更绿色的分子氧气为氧化剂，模拟手性非血红素酶催化剂引发的不对称催化氧化反应却仍然滞后。本项目在目前文献报道的几种高效非血红素酶模型配合物的基础上，对其进行手性修饰，探讨其与仿生协同底物共作用或单独作用活化分子氧的不对称催化氧化反应，为手性非血红素酶催化剂活化分子氧的不对称催化氧化反应奠定一定的基础。

发展了新型手性非血红素配合物相关配体TPA及其类似物、H-dpaq及卡宾吡啶钳式配体化合物库的构建，并运用现代光谱技术对其结构进行表征，遗憾的是本项目在研究其与廉价金属作用，在不对称仿生催化反应中的应用时并未取得较好的研究结果，目前对于该类手性配体在不对称催化反应中的应用仍在探寻之中；发展了含氟共轭烯炔多样性导向合成方法学，为一系列含氟杂环、含氟碳环的高效构建提供了简便的合成方法；发展了一条可规模化制备新型手性单膦配体Ming-Phos的工艺路线，为Ming-Phos的商品化奠定了基础；发展了钯催化环己二烯胺衍生物与芳基、烯基卤化物的不对称Heck/Tsuji-Trost反应，为手性六氢吲哚化合物骨架的高效构建提供了简便的合成方法。本项目发表标注国家自然科学基金项目批准号的期刊论文7篇，相关授权中国专利2项。