Organometallic Chemistry of Heterocycles

在这个由化学部化学催化项目资助的项目中，罗切斯特大学的William Jones教授正在研究新的反应，这些反应可以用来制造生物学和制药工业感兴趣的有机化合物。为了实现这一目标，人们正在研究过渡金属催化剂的基本反应，这些反应可以用来从现成的、廉价的起始材料中形成杂环。琼斯教授也在研究一种新的催化剂，这种催化剂可以打破开放的杂环并改变它们的结构。这项工作的更广泛影响包括向高中生推广，以吸引他们对STEM相关领域的职业感兴趣，以及开发通往具有制药重要性的中间体的新工艺。将详细的物理-有机金属背景与如何将现代计算方法应用于这些问题的理解相结合，为美国化学工业培养出训练有素的科学家。该项目的一个具体目标是通过“协同金属-去质子化”途径来研究环金属化的基本方面，这种途径现在在有机合成方法中很流行，以产生杂环。这些环金属化研究揭示了这些分子如何影响化学转化的基本方面，并为控制对所需产物形成至关重要的选择性提供了见解。第二个目标是开发目前普遍观察到的基于过渡金属的碳硫键裂解含硫分子的用途。一种应用是将可逆碳硫活化催化剂固定在固体载体上，使这种材料充当“硫海绵”，从而在燃烧前清理碳氢化合物燃料。

In this project funded by the Chemical Catalysis program of the Chemistry Division, Professor William Jones of the University of Rochester is examining new reactions that can be used to make organic compounds of interest in biology and the pharmaceutical industry. To accomplish this, fundamental reactions of transition metal catalysts are being examined that can be used to form heterocycles from readily available, inexpensive starting materials. Professor Jones is also examining new catalysts that can break open heterocycles and allow their structures to be altered.The broader impacts of this work include outreach to high school students to attract interest to careers in STEM related fields, as well as the development of new processes for routes to intermediates of pharmaceutical importance. The combination of a detailed physical-organometallic background combined with an understanding of how to apply modern computational methods to these problems produces extremely well trained scientists for the US chemical industry. One specific goal of this project is to examine fundamental aspects of cyclometallation via the "Concerted Metallation-Deprotonation" pathway that is now popular in organic synthetic methodology to produce heterocycles. These cyclometallation studies are revealing fundamental aspects of how these molecules effect the chemical transformations, and are providing insight into the control of the selectivity that is critical to formation of the desired product. A second goal is to develop uses for the now commonly observed transition metal based carbon-sulfur bond cleavage sulfur-containing molecules. One application involves anchoring a reversible carbon-sulfur activation catalyst to a solid support that allows this material to act as a "sulfur sponge," thereby permitting the cleanup of hydrocarbon fuels prior to combustion.