Molecular Recognition for Highly Regioselective Oxidation Catalysis

耶鲁大学的Robert Crabtree教授得到了无机，生物无机和有机化学计划的支持，以开发选择性氧化催化剂，该催化剂利用分子识别来定位立体控制氧化的远程底物。卟啉和三联吡啶与持有三酸识别元素的连接器作为螯合配体，以决定基板的几何形状相对于催化Mn或Fe网站。 目标氧化位点包括远离系链的C-H键，其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的底物，如含有多个CH键的二氢胆固醇。将催化剂结合到二氧化钛表面提供了用这些试剂实现多相催化的机会。 开发高效的氧化催化剂对于本体和精细化工过程都是重要的。 该奖项支持的学生将接触到广泛的化学技术，这些技术在催化中很重要，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.