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

化学催化项目支持罗彻斯特大学William D. Jones教授对均相过渡金属配合物在杂环化合物中切割和形成碳硫（C-S）和碳氮（C-N）键的研究。硫的研究主要应用于深度加氢脱硫（deep HDS）反应，而氮的研究主要是利用含有导向基团的分子中的亲电性C-H键激活来合成杂环。具体而言，研究人员获得了强键和/或阻碍键（X = S或N）裂解的动力学和热力学信息，提供了关于C-X键裂解和形成机制的信息，利用密度泛函理论（DFT）了解键裂解反应的机制，并开发了新的催化系统来操纵C-S和C-N键。该研究项目的重点是开发新的合成路线来制造含氮杂环，这是许多生物重要化合物的基本组成部分。过渡金属基催化剂也可能对通往具有重要医药意义的中间体的新路线产生影响。在学习如何选择性地打破碳硫键与碳氢键或碳碳键的过程中，琼斯教授和他的研究生和本科生为满足美国环保署关于燃料低硫排放的新标准做出了贡献。我们鼓励汉普顿大学的硕士研究生参与这个研究项目，并可以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.