Synthesis Of Polysubstituted Cyclohexadienes And Phenolic Compounds Based On [Ru] And [Pt]-catalyzed Cyclization Of Enynes

In recent years,the research on the synthesis of cyclic compounds by the cyclization of ene-ynes has been one of the research hotspots in organic synthesis methodology.The advantages of this type of reaction are mainly that the amount of catalyst is small,some cyclic compounds that are difficult to synthesize by traditional methods can be synthesized efficiently,and the side reactions are few and the synthesis of raw materials is relatively simple.From the research results reported so far,it can be seen that the more mature types of cycloaddition reactions are mainly Alder-ene reaction,1,3-dipolar addition reaction and [2+2+2] cycloaddition reaction.And other related reactions.And this article is mainly aimed at the diversity of products in the current research of enyne cyclization reactions,and respectively proposes the use of [Ru] metal complexes to catalyze the enyne [2+2+2]cycloaddition reaction to synthesize polysubstituted cyclohexanedi Study on the ene reaction and the synthesis of polysubstituted phenolic compounds using metal platinum catalyzed eneyne.Work 1: Ruthenium-catalyzed [2+2+2] cycloaddition reaction of diacetylene and its mechanism research.We used traditional nucleophilic substitution reaction and other methods to synthesize diacetylene reaction raw materials,and synthesized a series of polysubstituted cyclohexadiene products(sulfonamide octahydropyrrole and indole compounds).The mechanism control experiment showed that the catalyst of the reaction was first combined with the diacetylenic functional group to form a metal cyclopentadiene complex intermediate,and then through the insertion reaction of the alkene part,and finally through the route of metal reduction and elimination,the synthesis Series of target compounds.In addition,during the research process,we also found that when one of the propargyl sites of the substrate has geminal dimethyl groups,there is no significant change in the reaction yield,and when both propargyl sites have geminal dimethyl groups,In the case of methyl,the reaction will be hindered due to steric hindrance,making the reaction impossible.Work 2: Platinum-catalyzed isomerization of furane and alkyne rings.In this work,we continued the research direction of the previous work,and improved the1,6-enyne compound,upgraded the olefin part to a more stable furan structure,and used the two double bonds on the furan ring to interact with the intramolecular The alkyne part of the compound undergoes the corresponding cyclization reaction to synthesize a series of substituted phenolic compounds.From the catalytic results,it can be seen that since the two double bonds in the furan ring are not restricted,both can proceed to the first step of the complexation reaction with the metal,so that the reaction product finally exhibits two results,but the reaction is still relatively pure.Due to the existence of the furan ring,the reaction is affected by the large conjugated system in the furan ring.The cracking of the double bond presents an irregular state.After the metal complex of cyclopentene is formed in the first step,the carbon-oxygen bond can be Splitting in two directions resulted in the formation of two ring-isomerized phenolic compounds.The two topics in this article are both based on the 1,n-enyne ring isomerization reaction catalyzed by metal complexes.Through the redesign of the enyne substrate and the use of different reaction structures,two As a result of different reaction pathways,the cycloisomerization reaction of enynes is further improved,the structure of the product is enriched,and a method for synthesizing the structure of cyclohexadiene and phenolic compounds is provided.Through the research ideas in this article,we can further develop more new cyclization reactions in the direction of1,n-enyne ring isomerization reactions.