Molecular Recognition for Highly Regioselective Oxidation Catalysis

耶鲁大学的Robert Crabtree教授在无机、生物无机和有机金属化学项目的支持下，开发了选择性氧化催化剂，利用分子识别来定位远程底物进行立体控制氧化。卟啉和带有三酸识别元素的连接体的三联吡啶作为螯合配体来决定相对于催化Mn或Fe位点的底物几何形状。目标氧化位点包括远离系链的C-H键，这些键将立体选择性地转化为醇产物。该项目包括机械测试和扩展到复杂底物，如含有多个CH键的二氢胆固醇。将催化剂与二氧化钛表面结合为实现这些试剂的多相催化提供了机会。开发高效的氧化催化剂对于大宗化工和精细化工都具有重要意义。该奖项支持的学生将接触到广泛的化学技术，这些技术在催化方面很重要，他们将利用配位化学知识和有机合成技能。

Professor Robert Crabtree of Yale University is supported by the Inorganic, Bioinorganic and Organometallic Chemistry program to develop selective oxidation catalysts that utilize molecular recognition to position a remote substrate for stereocontrolled oxidation. Porphyrins and terpyridines with a linker holding a triacid recognition element serve as chelating ligands to dictate substrate geometry relative to the catalytic Mn or Fe site. Target oxidation sites include C-H bonds remote from the tether that will be stereoselectively converted to alcohol products. This project includes mechanistic tests and extensions to complex substrates like dihydrocholesterol that contain multiple CH bonds. Binding the catalysts to a titanium dioxide surface provides opportunities for realizing heterogeneous catalysis with these reagents. Development of efficient oxidation catalysts is important for both bulk and fine chemical processes. Students supported by this award will be exposed to a wide range of chemical techniques that are important in catalysis, and they will utilize both coordination chemistry knowledge and organic synthetic skills.