铁催化的烷烃选择性仿生氧化

The development of selective oxidation of alkane has been one of the most important goals over the years. The traditional chemocatalysis for alkane oxidation needs vigorous conditions with low selectivity, high energy consumption and serious environmental pollution, which cannot meet the requirements of current situation and development of chemical industry. Biomimetic catalysis for alkane oxidation has attracted increasing attention recently due to its high efficiency, high selectivity, mild conditions and low cost. However, current biomimetic catalysis for alkane oxidation focuses on porphyrin catalyst, but with some limitations, such as high cost ligand synthesis, and low tunability. It is very difficult to obtain the selective oxidation of various C-H bonds of alkane (3°, 2°and 1° C-H), especially the selective oxidation of terminal C-H bond of alkane. This project will focus on the development of some novel non-heme catalysts for selective oxidation of various alkane C-H bonds. Finally, we will try to realize the selective oxidation of terminal C-H bond of normal hexane and other long-chain alkanes for the bio-synthesis of bulk chemical raw materials, such as adipic acid and long-chain alcohols.

烷烃的选择性氧化是人们长期以来研究的重要目标之一。传统的化学催化氧化，由于剧烈的反应条件、低选择性、高能耗和环境污染，已经远远不能满足现代化学工业发展的需要。仿生催化由于高效、高选择性、温和、经济等多种优势最近受到了日益广泛的重视。然而目前研究较多的卟啉类仿生催化氧化研究由于催化剂高的合成成本，不易调控等局限，很难实现烷烃各类C-H键（3°、2°和1°）的选择性催化氧化，特别是具有重要应用价值的烷烃的末端1° C-H氧化。本项目拟发展一类新型结构的非卟啉铁类仿生催化剂，利用位阻调控的方式实现烷烃各类C-H的选择性氧化，特别是烷烃的末端氧化；同时尝试利用正己烷和长链烷烃的选择性末端氧化进行己二酸和长链醇等一些大宗化工原料的仿生合成。

我们围绕烷烃的选择性氧化这一目标进行了催化剂的精心设计和广泛尝试，但是目前还没有取得烷烃选择性控制的突破。通过调整目标，我们发现这些催化剂可以应用于其他类型键的活化如C=C，含杂原子的C-H和C-C键，并获得的三类催化模式和多个类型反应的突破，包括Ni/Fe类单金属催化烯烃的直接官能化反应；Ni和布氏酸协同催化的烯烃和醛的氢酰基化反应；Ni和Al共催化的C-H和C-C的催化活化。为一些长期存在的反应难题提供了解决办法，而且为我们下一步继续完成简单烷烃的选择性氧化奠定了坚实的基础。