不饱和羧酸的亲电或自由基氟烷基化以及氟化脱羧反应研究

The widespread use of the fluorinated organic compounds in many fields such as materials, medicine and agrochemicals has intrigued the development of numerous new methods for the incorporation of fluorine into organic molecules. Most of the contributions in this field, however, focus on the reactions between the fluorinating agents or fluoroalkylating agents and substrates such as alkenes, arenes, boronic acids, organic halides, aldehydes, ketones, and so on, whereas little attention has been paid on the fluorination and fluoroalkylation of carboxylic acids, an important class of organic compounds that are not only abundant in the nature, but also can be conveniently prepared in large scale. On the basis of our preliminary achievement on fluoroalkylative decarboxylation, this research proposal aims at the systematic study of electrophilic (or radical) fluorinative and fluoroalkylative decarboxylation reactions of an array of unsaturated carboxylic acids in the following three aspects: (1) the investigation on the influence of carboxylic acid structures on the decarboxylation manner with the same fluorinating agent or fluoroalkylating agent; (2) the investigation on the influence of fluorinating agents or fluoroalkylating agents on the reaction pathway using the same carboxylic acid; (3) a global summarization of the reaction characteristics and governed rules in the aforementioned decarboxylative transformation with different electrophilic (or radical) fluoroalkylating agents.

随着有机含氟化合物在材料，医药，农药等领域的广泛应用，新的氟化方法的开发已经成为一个热门的研究领域。综观所有已经发表的氟化和氟烷基化的研究工作可以发现，人们关注更多的以是烯烃、芳烃、硼酸、卤代物、醛、酮等作为底物来进行氟化或者氟烷基化研究，但是很少有人将羧酸这样一类自然界大量存在同时也很容易大量制备的原料作为底物来进行氟化或者氟烷基化研究。本项目将在已有的工作基础上，重点围绕不饱和羧酸的亲电或自由基氟烷基化以及氟化脱羧反应，对下面几个方面进行研究:（1）考察在同一氟烷基化（或氟化）试剂条件下, 不饱和羧酸结构类型的改变对该反应的影响；（2）考察在同一结构类型不饱和羧酸条件下，不同的氟烷基化（或氟化）试剂的对该反应的影响；（3）全面的总结不同结构的亲电（或自由基）氟烷基化试剂的反应特性和规律。

本项目围绕不饱和羧酸的亲电或自由基氟烷基化以及氟化脱羧反应，完成了下面几项研究内容：.（1）完成了三种新型含氟烷基亚磺酸钠盐的制备，并且以烯基取代的芳基磺酰亚胺作为底物，对三种含氟烷基亚磺酸钠盐的反应活性进行了研究，研究结果表明含氟烷基 . 亚磺酸钠盐是很好的自由基试剂，并且揭示了三种含氟烷基亚磺酸钠盐的反应活性差异；.（2）完成了β,γ-不饱和羧酸的亲电三氟甲基化脱羧反应研究，拓展了该类羧酸对亲电氟烷基化试剂的反应范围；.（3）完成了β-酮酸的亲电氟化脱羧反应研究，也对其反应机理进行了研究，进一步拓展了不饱和羧酸的类型；