Molecular Recognition for Highly Regioselective Oxidation Catalysis

耶鲁大学的罗伯特·克拉布特里教授得到了无机化学、生物无机化学和金属有机化学计划的支持，开发了选择性氧化催化剂，利用分子识别来定位远程底物，用于立体控制的氧化。带有带有三酸识别元件的连接体的卟啉和三联吡啶作为螯合配体来决定底物相对于催化的锰或铁中心的几何构型。目标氧化位置包括远离系绳的C-H键，这些C-H键将被立体选择性地转化为酒精产品。该项目包括机械测试和对复杂底物的扩展，如包含多个CH键的二氢胆固醇。将催化剂结合到二氧化钛表面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大宗和精细化工过程都具有重要意义。获得该奖项支持的学生将接触到在催化中重要的广泛的化学技术，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.