Electrochemically induced fluoride umpolung

亲电氟化剂通常具有N-F键，其本身通常是由极危险的氟气体在氮中心的作用形成的。将测试各种胺的阳极氧化是否能产生胺自由基或能与原位氟离子反应形成所需N-F键的指示。候选胺将首先通过在理论DFT水平上检查选定胺系统的单电子和双电子氧化的热力学以及随后的N-F键形成，以及计算被氧化物质的电子分布来筛选。然后将合成有希望的候选物质，并进行循环伏安法和计时安培法测量，以收集氧化电位等经验数据，与理论值进行比较，并帮助确定氟存在下可能的电化学反应结果。如果N-F键以所需的电化学方式提供，希望该方法可以应用于[18F]氟离子，以方便地生成18F标记的氟化剂。

Electrophilic fluorinating agents typically possess a N-F bond, itself typically forged by the action of extremely hazardous fluorine gas at a nitrogen centre. It will be tested whether anodic oxidation of various amines can generate aminium radicals or dications capable of reacting with in situ fluoride ions to form the desired N-F bond. Candidate amines will first be screened by examining at the DFT level of theory the thermodynamics of one- and two-electron oxidations of selected amine systems and subsequent N-F bond formation, as well as calculating electronic distributions of the oxidised species. Promising candidates will then be synthesised and subjected to cyclic voltammetric and chronoamperometric measurements to gather empirical data such as oxidation potentials to compare with theoretical values, as well as to aid in the determination of possible electrochemical reaction outcomes in the presence of fluoride. If N-F bonds are furnished in the desired electrochemical fashion, it is hoped that the methodology can be applied to [18F]fluoride ions to conveniently generate 18F-labelled fluorinating agents.