Cleavage and Formation of C-S and C-N Bonds in Heterocyclic Compounds by Homogeneous Transition Metal Complexes

化学催化计划支持罗切斯特大学的威廉·D·琼斯教授关于均相过渡金属络合物在杂环化合物中裂解和形成碳-硫(C-S)和碳-氮(C-N)键的研究。硫的研究在深度加氢脱硫反应中具有应用价值，而氮的研究主要集中在利用分子中的亲电C-H键活化含直接基团的分子合成杂环。具体地说，研究人员获得了强和/或受阻的C-X键(X=S或N)断裂的动力学和热力学信息，提供了C-X键断裂和形成机理的信息，利用密度泛函理论(DFT)了解键断裂反应的机理，并开发了操纵C-S和C-N键的新催化体系。这个研究项目的重点是开发新的合成路线来制造含氮杂环，这些杂环是许多生物重要化合物的基本构件。以过渡金属为基础的催化剂也可能对医药中间体的新路线产生影响。在学习如何有选择地打破碳-硫和碳氢或碳-碳键的过程中，琼斯教授和他的研究生和本科生为达到美国环保局关于燃料低硫排放的新标准做出了贡献。汉普顿大学的硕士研究生被鼓励参与这一研究项目，并可直接被罗切斯特大学的博士项目录取。麦克奈尔学者和NSF REU的学生也为研究工作做出了贡献。

The Chemical Catalysis Program supports the research of Professor William D. Jones of the University of Rochester on the cleavage and formation of carbon-sulfur (C-S) and carbon-nitrogen (C-N) bonds in heterocycle compounds by homogeneous transition metal complexes. The studies with sulfur have applications in deep hydrodesulfurization (deep HDS) reactions while the studies with nitrogen focus on the use of electrophilic C-H bond activation in molecules containing directing groups for heterocycle synthesis. Specifically, the researchers obtain kinetic and thermodynamic information on the cleavage of strong and/or hindered C-X bonds (X = S or N), provide information about the mechanisms for C-X bond cleavage and formation, work to understand the mechanism of the bond cleavage reactions using density functional theory (DFT), and develop new catalytic systems for the manipulation of C-S and C-N bonds. This research project is focused on the development of new synthetic routes to make nitrogen-containing heterocycles, which are fundamental building blocks in many biologically-important compounds. The transition metal-based catalysts may also have an impact on new routes towards intermediates of pharmaceutical importance. In learning how to selectively break carbon-sulfur versus carbon-hydrogen or carbon-carbon bonds, Professor Jones and his graduate and undergraduate students contribute to meeting new EPA standards for low sulfur emissions from fuels. Master's level graduate students from Hampton University are encouraged to participate in this research project and can be accepted directly into the Ph.D. Program at the University of Rochester. McNair Scholars and NSF REU students also contribute to the research efforts.