Green Synthesis And Application Of Isoindoline And Thioethylene-oxide

In recent decades,with the rapid development of organic chemistry,the research of the difunctionlization of carbon-carbon unsaturated bonds has attracted much attention of many chemists,and much progress has also been achieved.Olefins and alkynes are widely used in organic synthesis due to their high reactivity,low cost and availability,and their ability to be convered into multiple functional groups.Difunctionalization of alkenes and alkynes allows the introduction of new and different functional groups at both ends of double and triple bonds by a one-pot method to construct"new"compounds with high efficiency and high selectivity.Therefore,the functionalization of unsaturated hydrocarbons plays an irreplaceable role in the fields of natural products,material chemistry,medicine,dyes and other organic synthesis.However,the traditional difunctionalization of carbon-carbon unsaturated bonds requires the addition of excessive air and moisture sensitive organometallic reagents,high reaction temperatures,or expensive metal catalysts,which hinders the further development of this field.Therefore,it is of great significance to further construction of bioactive compounds under mild reaction conditions through the difunctionalization of carbon-carbon unsaturated bonds.In this thesis,the synthesis of methyl2-（3-oxoisoindolin-1-ylidene）acetates and 3-（（aryl/alkyl thiyl）methyl）ethylene oxide has been successfully achieved through the difunctionalization of alkynes and alkenes under mild reaction conditions.The main contents of this thesis include the following two parts:（1）Investigation on the amine-carboxylation of o-alkynylamides with CO₂A base promoted sequential cyclization and carboxylation of o-alkynylamides with CO₂ has been achieved,to furnish diverse functionalized2-（3-oxoisoindolin-1-ylidene）acetateswithhigh regioselectivity in good yields.This approach begins with the amide anion undergoes 5-exo-dig cyclization,leading to the formation of vinylic anion intermediate,followed by the nucleophilic addition to CO₂ to afford the desired products.Under the optimized reaction conditions,1 mmol scale reaction was carried out,and the desired product could be isolated in 64%yield.In addition,the product can be further transformed into potentially drug-active structures,which further proves the practicality of this reaction.Thus,it provides a simple and straightforward method to diverse biologically important isoindolinones by using CO₂ as the carboxylic source.（2）Investigation on the oxysulfenylation of allyl alcohols with N-（aryl/alkyl thio）succinimidesThe oxysulfenylation of allyl alcohols with N-（aryl/alkyl thio）succinimides by using HFIP as the solvent to afford a series of 3-（（aryl/alkyl thiyl）methyl）ethylene oxide compounds at moderate to good yields.It was worth noting that the reaction does not require any transition metal catalysts or any other additives.Moreover,this procedure tolerates some functional groups well and features the good functional group tolerance.In addition,the product can be further transformed into potentially drug-active structures,which further proves the practicality of this reaction.