Transition metal assisted fluorinations

在这个由化学系化学合成计划资助的项目中，路易斯维尔大学化学系的Gerald B.Hammond教授将研究氟金活化过程，这些过程可以中介串联序列，导致新的金属亲核加成/偶合/氟化反应，这反过来将导致有机氟化合物的高效合成。尽管氟有一种独特的能力来改变化合物的物理化学性质，但它在小分子上的引入通常是麻烦的。事实上，氟化脂肪族和环状体系的合成需要繁琐的试剂或合成过程，这些合成过程依赖于一小部分商业含氟构件。这项研究的基于机理的方法将能够以药物化学友好的方式合成脂肪族有机氟化合物，如氟酮和含氟杂环化合物，利用能够进行金属介导的氟化、氧化或偶联的阳离子金属物种，以及容易获得的炔烃或烯烃作为起始原料。最终，关于氟生成的阳离子物种的拟议工作将对氟和过渡金属的相互作用产生实质性的见解。该项目的更广泛影响是，其定义明确的模块适合于培训年轻一代的有机氟化学学生和博士后研究员，与其他工业化国家相比，有机氟化学是一个由少数美国科学家从事的研究领域，尽管氟在医药或农业化学领域的重要性与日俱增。该项目将对制造领域产生广泛的影响，因为它将以多样化的方式和更少的合成步骤随时获得含氟化合物。

In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Gerald B. Hammond of the Department of Chemistry at the University of Louisville will investigate fluorine-gold activation processes that can mediate tandem sequences leading to novel metal-mediated nucleophilic addition/coupling/fluorination reactions, which, in turn, should lead to efficient synthesis of organofluoro compounds. Even though fluorine has a unique ability to modify the physico-chemical properties of a compound, its introduction on small molecules is usually cumbersome. Indeed, the syntheses of fluorinated aliphatic and cyclic systems require tedious reagents or synthetic procedures that rely on a small pool of commercial fluorine-containing building blocks. The mechanism-based approach of this research will enable the synthesis of aliphatic organofluoro compounds, such as fluoroketones and fluoroheterocycles in a medicinal chemistry-friendly manner, utilizing cationic metal species capable of metal-mediated fluorinations, oxidations or couplings, and readily available alkynes or alkenes as starting materials. Ultimately, the work proposed on fluorine-engendered cationic species will yield substantial insights on the interaction of fluorine and transition metals. The broader impact of this project is that its well-defined modules are suitable for training a younger generation of students and postdoctoral fellows in organofluorine chemistry, a research area that is performed by a handful of scientists in the U.S., compared to other industrialized nations, despite the ever-increasing importance of fluorine in the medicinal or agrochemical fields. This project will impact the manufacturing field broadly defined because it will give ready access to fluorinated compounds in a diversified manner and with fewer synthetic steps.