Catalytic, Regioselective Functionalization of Alkanes and Arenes

无机化学、生物无机化学和金属有机化学项目的这一奖项支持耶鲁大学的John F.Hartwig博士的研究，目的是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，并开发烷烃和芳烃功能化的新方法。该项目旨在了解硼基如何创建对C-H键断裂具有异常反应的金属中心，以及C-H键活化的中间体如何创建功能化产品。还将评估与官能化底物和聚烯烃反应的合成潜力。具体地说，将研究用取代环戊二烯基以外的阴离子配体修饰的Ru催化剂和具有五甲基环戊二烯配体的Ru催化剂，以确定产生烷烃和芳烃官能化活性的催化剂结构的特征。由于小分子烷烃的硼化反应可以扩展到受保护的官能化底物的硼化反应和聚烯烃的硼化反应，这些反应将作为在复杂分子中进行甲基选择性官能化和生成在侧链末端含有各种官能团的原型聚烯烃的重要步骤而发展。将碳氢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。特别是，烷烃转化为直链醇、胺和羧酸是合成有机化学中的一个重要目标。这项工作利用了哈特威格发现的一种催化系统，这种催化系统只需两步就能从烷烃中产生线性官能化产物。该项目还将研究融入到学生和博士后更广泛的教育经验中，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.