Catalytic, Regioselective Functionalization of Alkanes and Arenes

这个奖项在无机，生物无机和有机化学计划支持研究博士约翰F。Hartwig的研究，以了解硼烷试剂和金属硼基中间体对烷烃和芳烃C-H键的有效裂解和官能化，并开发烷烃和芳烃官能化的新方法。该项目旨在了解硼基如何产生对C-H键断裂具有异常反应性的金属中心，以及C-H键活化的中间体如何产生功能化产物。 还将评估与官能化基材和聚烯烃反应的合成潜力。具体而言，铑催化剂改性的阴离子配体而不是取代的取代基和钌催化剂与pentamethylpyrene配体将被研究，以确定的催化剂结构的功能，创造活性的烷烃和芳烃的官能化。 由于小烷烃的硼基化可以扩展到受保护的官能化底物的硼基化和聚烯烃的硼基化，这些反应将被开发为对复杂分子中的甲基进行选择性官能化和产生在侧链末端含有各种官能团的原型聚烯烃的重要步骤。将烃键直接转化为有用的化学品和药物是一个具有实验室和经济意义的目标。 特别地，烷烃转化为直链醇、胺和羧酸是合成有机化学中的突出目标。 这项工作利用了Hartwig发现的催化体系，该催化体系只需两步就可以从烷烃中生成线性官能化产物。 该项目还将研究纳入学生和博士后更广泛的教育体验，并为他们提供先进催化方法的培训。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Dr. John F. Hartwig of Yale University to understand the efficient cleavage and functionalization of alkane and arene C-H bonds by borane reagents and metal boryl intermediates and to exploit a new approach to alkane and arene functionalization. The project aims to understand how boryl groups create metal centers that are unusually reactive toward C-H bond cleavage and how the intermediates from C-H bond activation create functionalized products. The synthetic potential for reactions with functionalized substrates and polyolefins will also be evaluated. Specifically, rhodium catalysts modified with anionic ligands other than substituted cyclopentadienyl groups and ruthenium catalysts with pentamethylcyclopentadienyl ligands will be studied to identify the features of the catalyst structure that create activity for the functionalization of alkanes and arenes. As the borylation of small alkanes can be extended to the borylation of protected, functionalized substrates and to the borylation of polyolefins, these reactions will be developed as an important step toward conducting selective functionalization of methyl groups in a complex molecule and toward generating prototype polyolefins that contain a variety of functional groups at the termini of sidechains. Directly transforming hydrocarbon bonds into useful chemicals and pharmaceuticals is a goal of both laboratory and economic significance. In particular, the conversion of alkanes to linear alcohols, amines and carboxylic acids is a prominent goal in synthetic organic chemistry. This work capitalizes on Hartwig's discovery of a catalytic system that generates linear functionalized products from alkanes in only two steps. This project also integrates research into a broader educational experience for both students and postdocs and provides them with training in advanced catalytic methods.