蝎基晶态多孔材料催化的非均相烯烃α位碳氢键活化研究

Transition metal catalyzed direct C-H bond functionalization is of tremendous scientific value and is one of the core topics in the field of catalysis research. This project will take a unique approach, using heterogeneous catalysts to solve this frontier scientific problem. The main focus is the selective activation of allylic C-H bonds using metal-organic framework materials with unique scorpionate active centers. The self-assembly during solvothermal crystallization strongly favors the formation of metastable phases hence provides opportunities in synthesizing unique scorpionate structures that are inaccessible in solution chemistry. Relying on the unique scorpionate active centers composed of base transition metals, the activation of allylic C-H bonds will be realized. We will especially focus on the post-modification of allylic sites in pharmaceutical intermediates and natural products in order to achieve high added-value conversions. While obtaining high activity and high chemo-selectivity, the stability of the catalytic site is stabilized by the heterogeneous nature of the crystalline framework structure. And the turnover number of the catalyst is greatly increased, thereby achieving high activity and high stability simultaneously. This project tackles the current challenges of base metal C-H activation from a unique aspect and well combines inorganic chemistry and organic synthetic methodology studies. This study will open up the new horizon for the C-H bond activation research community, and lead to the next generation of efficient, inexpensive and durable catalysts.

过渡金属催化的碳氢键直接官能化是催化研究领域的核心课题之一，具备极高的科学意义和社会价值。本项目将独辟蹊径，利用多相催化剂解决这一前沿科学问题，着重研究具备蝎基活性中心的金属有机框架材料对烯烃α位碳氢键的选择性活化。旨在利用溶剂热结晶自组装的方法，诱导生成介稳相，并合成小分子化学领域中难以获得的独特蝎基化学结构。依托由廉价过渡金属构成的独特蝎基活性中心，采用金属有机催化方法学的研究手段，催化活化烯烃α位碳氢键，尤其着重研究医药中间体和复杂天然产物中烯烃α位的后修饰，实现高附加值转化。在得到高活性、高化学选择性催化剂的同时，利用晶态骨架结构对催化活性位的锚泊稳定，大幅提升催化剂的回转数，进而解决高活性催化剂难以维持催化回转数的难题。本项目的开展从非均相催化的独特视角出发，融合无机合成学和有机合成方法学研究手段，为制备高效、廉价、耐用的碳氢键活化催化剂提供新的合成学途径，为学界开辟崭新的视野。

过渡金属催化的碳氢键直接官能化是催化研究领域的核心问题之一，具有极高的科学意义和社会价值。本项目研究基于金属有机框架材料溶剂热合成中易于生成介稳相化合物的特点，利用活性位后修饰的精准合成手段，首次构造了溶液化学中追求多年而不可得的独特局部化学结构，并利用外配位圈活化原理，将氢原子转移HAA化学与金属有机化学引入到多孔材料催化平台。利用独特多孔晶态催化剂，针对碳氢键活化这一科学"圣杯"级难题开展研究。在限域空间中利用反应底物与催化位点的配位能力，极大程度地提高了催化剂回转数的同时，巧妙生成动力学选择性产物，实现了催化碳氢键活化的化学选择性以及区域选择性。从非均相催化剂角度出发，在均相、分子催化所未能实现的催化反应中为问题的解决提供更可靠的途径，为学界提供崭新的视野。