Study On The Synthesis Of Novel Organic Selenium Compounds Based On Electrochemical Mediated Gemdiselenation Of Sulfoxide Ylide

Background:Selenium(Se)is an element that is indispensable to humans and animals discovered in1817 by the Swedish chemist Joens Jacob Bezelius.Because the content of selenium in the earth’s crust is very low(0.05 ppm),it is regarded as a trace element.Selenium exists in both organic and inorganic forms.Inorganic forms include elemental selenium,metal selenides,and selenate;in organic forms,selenium is combined with carbon(methyl compound,selenoamino acid,selenoprotein)or selenium and carbon(selenomethionine).,Selenocysteine)covalently bound compound.By consulting related reports,we found that organic selenides are generally less toxic than inorganic selenides and are commonly found in biological samples.In addition,organic selenides play an increasingly important role in the field of biomedicine,such as anti-tumor,anti-cancer,Anti-inflammatory,etc.Therefore,it is particularly important to develop some new strategies to effectively construct new organic selenium compounds.The main methods of traditional synthesis of organic selenium compounds usually require expensive transition metals,equivalent additional oxidants or other environmentally unfriendly chemical reagents.However,with the rapid development of synthetic chemistry,environmental problems have gradually become more serious.In this context,The development of some new,green and efficient new strategies for the synthesis of organic selenides has become one of the current hotspots.In recent years,some emerging synthetic strategies have begun to enter the attention of chemists.Among them,electrochemical strategies have received wide attention from many scientific researchers due to their unique advantages.Sulfur ylide-has a carbanion structure stabilized by an adjacent positive sulfide ion.According to its chemical structure,it can be divided into four categories: sulfur ylide,sulfoxide ylide,sulfonyl ylide,and sulfonyl ylide.Such compounds are often used as substrates for alkylation reactions or acylation reactions,and the resulting products usually have higher stability and practicability.In addition,such compounds are also used in epoxidation,nitridation,rearrangement and alkene It has a wide range of applications in chemical reactions.Therefore,we tried to construct a series of selenium compounds with potential medicinal value by using sulfoxide ylide and diselenide as substrates based on the new reaction mode of electrochemical oxidation strategy.Objective:1.Starting from compounds with carboxylic acid groups,construct a series of sulfoxide ylide compounds;at the same time,synthesize a series of diselenide substrates with different electronic effect substituents,and perform simple structural confirmation of these compounds.2.Using the reaction mode of electrochemical oxidation strategy,try to realize the selenization reaction between sulfoxide ylide and diselenide substrate,and optimize the reaction to obtain a series of organic selenides with relatively good yields.3.Apply the above synthesis strategy to some biologically active drug molecule derivative structures,efficiently construct a series of organic selenium compounds with potential medicinal value,and investigate the stability and practicability of these compounds.Methods:1.Through the chlorination of the carboxylic acid substrate and further coupling it with trimethyl sulfoxide iodide,construct sulfoxide ylide substrates with different substituents.The structure of the synthesized product was characterized by nuclear magnetic resonance and high-resolution mass spectrometry.2.The non-separated reaction tank is a container,graphite is used as anode,platinum is used as cathode,and tetrabutylammonium iodide is used as electrolyte.Through constant current electrolysis of sulfoxide ylide and diselenide substrates at room temperature,a series of6 twins are constructed.Selenium compounds,and through the control experiment and free radical capture experiment to in-depth discussion of the reaction mechanism.Results:We use electrochemical oxidation strategy as the key technology to synthesize 31 gemdiselium compounds substituted with different functional groups,which provides a green and efficient synthetic pathway and compound basis for constructing a lead compound library of potential antitumor drugs.These compounds are characterized by nuclear magnetic resonance and high-resolution mass spectrometry.In addition,through exploration,we have found that the construction of these compounds can also be achieved under air oxidation conditions.Therefore,we use two different A comparison of these compounds was made with the reaction conditions of,and it was finally found that the electrochemical oxidation strategy was better than the air oxidation strategy.And under the conditions of electro-oxidation,the reaction can also be prepared by the "one-pot method",starting from the carboxylic acid raw material,to achieve the gram-scale preparation,and the target product can be obtained with a yield of 63%.Through a series of mechanism experiments,we also have a general idea of the reaction mechanism to a certain extent.Conclusion:Based on the electrochemical strategy,a series of gem-diselenide compounds can be constructed stably,effectively and environmentally,and the electrochemical reaction strategy can be compatible with sulfoxide ylide substrates substituted with different functional groups and diselenide compounds with different substituents;however,Under the action of air oxidation,although the standard substrate can also achieve the production of the target product with a relatively high yield,it has shown poor results when it is universally investigated.Therefore,the electrochemical strategy is relatively better than the air oxidation strategy.In addition,the gram-level experimental results based on electrochemical conditions show that the electro-oxidation strategy has potential application value.In summary,we use the electrochemical oxidation strategy as the key technology to synthesize 31 gemdiselium compounds substituted with different functional groups,which provides a green and efficient synthesis pathway and compound basis for constructing a lead compound library of potential antitumor drugs.