【作者】 李浩；

【导师】 雷爱文；

【作者基本信息】 江西师范大学 ， 有机化学， 2023， 硕士

【摘要】 通过近些年的高速发展,电化学合成在有机合成当中扮演着越来越重要的角色。相比于传统的有机合成,电化学合成是一种更为绿色环保的合成手段。因为传统的合成步骤中,都不可避免地运用了化学计量的氧化剂或还原剂,这不可避免地产生了大量的废物,对环境造成了极大的危害。而电合成作为一种高效而温和的合成工具,通过电子的传递,无需外加的氧化和还原剂,就能够在阳极发生氧化反应,阴极实现还原反应。通过电化学氧化的方式,底物在电极表面通过阳极氧化发生单电子转移过程,产生高活性的自由基物种,之后再发生下一步的转化,可以轻松形成C-E键(E=C、N、S、Se、O、P和X等)。本论文通过电化学氧化的方式,成功实现了以下两个工作:1.通过电化学氧化二硒醚产生硒自由基,之后对带有不饱和双键的烯酰胺发生自由基串联环化反应,生成五元杂环硒取代的亚氨基苯并异呋喃。该反应可以兼容各种位点取代的烯酰胺,相较于传统亚氨基苯并异呋喃的合成方法,无需使用额外的氧化剂和添加剂,具有着清洁环保的优点。通过自由基捕获实验和循环伏安实验,进一步证实了提出的反应机理。2.通过电化学氧化脱氢偶联策略,在一体池中氧化糖基硫醇SH与另外一分子的硫醇SH,构建S-S键,生成糖基二硫化物。反应的同时,质子会在阴极释放有价值的氢气。氧化富电子芳烃CH和糖基硫醇SH,构建C-S键,生成富电子芳烃硫苷。该策略无需预官能团化的糖基硫化物,无需氧化剂,就可以生成不对称的糖基二硫化物和硫苷。反应可以构建各种不对称的糖基二硫化物,不同种类的糖基硫醇与半胱氨酸都能顺利发生偶联。更多还原

【Abstract】 Through rapid development in recent years,electrochemical synthesis has played an increasingly important role in organic synthesis.Compared to traditional organic synthesis,it is a more green and environmentally friendly organic synthesis method.Due to the inevitable use of stoichiometric oxidants or reducing agents in traditional synthesis steps,a large amount of waste is inevitably generated,causing significant harm to the environment.As an efficient and mild synthesis tool,electrosynthesis can undergo oxidation reactions at the anode and reduction reactions at the cathode through electron transfer without the need for additional oxidants and reducing agents.The substrate undergoes a single electron transfer process on the electrode surface through anodic oxidation,producing highly active free radical species.After that,the next step of transformation can easily form C-E bonds(E = C,N,S,Se,O,P,and X,etc.).This paper successfully achieved the following two tasks through electrochemical oxidation:1.Selenium free radicals are generated by electrochemical oxidation of diselenides,and then a series of free radical cyclization reactions are carried out on the substrate enamide with unsaturated double bonds,resulting in the formation of five membered heterocyclic selenium substituted iminobenzofuran.This reaction can be compatible with various site substituted enamides,and compared to the traditional synthesis method of iminobenzofuran,it does not require the use of additional oxidants and additives,and has the advantage of being clean and environmentally friendly.The proposed reaction mechanism was further demonstrated through free radical capture experiments and cyclic voltammetry experiments.2.Through the electrochemical oxidation dehydrogenation coupling strategy,the S-S bond is formed by oxidizing the glycosyl thiol SH with another molecule of thiol SH in an undivided cell,generating glycosyl disulfides.During the reaction,the proton will release valuable hydrogen at the cathode.Oxidize rich electron aromatic hydrocarbons CH and glycosyl thiols SH,construct C-S bonds,and generate rich electron aromatic glucosinolate.This strategy does not require pre-functionalized glycosyl sulfides or oxidants to generate asymmetric glycosyl disulfides and glucosinolate.Reactions can construct various asymmetric glycosyl disulfides,and different types of glycosyl thiols can smoothly couple with cysteine.更多还原