“负氟效应”规律指导下利用金属调控的氟烷基化反应研究

由于向目标分子中引入氟原子或者含氟片段往往可以带来有益的性质，因此许多新开发的医药以及农药分子中都含有氟。作为向分子中引入氟的一种重要途径，金属调控的氟烷基化反应已经成为当前一个研究热点。综观所有已发表的关于氟烷基化反应的研究工作，人们更多关注的是反应的实用性，而对反应的规律缺少总结。我们在导向选择性含氟物质合成的有机氟化学研究中,已经注意到过渡金属在调控α-氟代碳负离子反应性中起着重要作用。本项目将在我们提出的"负氟效应"这一关于氟代碳负离子反应规律的指导下，从以下三方面对金属调控的氟烷基化反应进行详细的研究：（1）不同金属调控下的同一氟烷基化反应（过渡金属效应）；（2）同一金属调控下的不同氟烷基化反应（氟原子取代效应）；（3）所总结出的规律在解决氟烷基化中一些难点问题上的应用。

Introduction of fluorine atom or fluorinated moiety often imparts beneficial properties to the target molecule, and a variety of fluorine-containing pharmaceuticals and agrochemicals have been developed. As a major method for introducing fluorine into organic molecules, metal-mediated fluoroalkylation has become a "hot" research topic in modern synthetic chemistry. However, most of the published work in this field focused on the development of practical synthetic methods, and little attention has been paid on the connection between different types of reactions. During our study of organofluorine chemistry directed towards the synthesis of selectively fluorinated organic compounds, we have noticed that transition metal effect plays an important role in mediating the reactivity of α-fluoro carbanion. Directed by "Negative Fluorine Effect" that was proposed by us, this research proposal aims at a comprehensive study of metal-mediated fluoroalkylation in the following three aspects: (1) the investigation of metal effect in the same fluoroalkylation; (2) the investigation of fluorine effect in the fluoroalkylation mediated by the same metal; (3) the application of our own-developed synthetic methodology in solving some of the long-standing challenges in fluoroalkylation chemistry.