Study Of The Palladium-Catalyzed Coupling Of Polyenes Containing Acryl Group And Aryl Halides

The pyrrole derivatives are the essential components of organism,and they are closely rerated to life activity.So it may be extremely significant that using the simple effective Heck reaction to synthesis the complex compounds containing the pyrrole or the pyrrolidinone ring.In this paper, the palladium-catalyzed coupling cyclic reaction was mainly investigated that polyenes containing the acryl group react with the aryl halides to synthesis the series of new compounds with the pyrrole skeleton.1.Palladium-catalyzed coupling cyclization of N-acryl-N-benzylcinna mamide and aryl halidesN-acryl-N-benzylcinnamamide reacts with the aryl halides(R-C₆H₄X,R =H,o-CH₃,p-CH₃,p-OCH₃,p-Cl,m-Cl,p-CN,p-CHO,p-COOCH(CH₃)₂, p-COOCH₂CH₃;X=I,Br,Cl)by the palladium acetate under the argon.The experiment results showed that the different products were got in high yields through controlling different reaction temperature.As the result of series of experiments,it gives 7 pyrrole diones derivatives:the double bond compounds,11 polycyclic compounds and 5 breaken bond compounds. When temperature is between 100-105℃,the primary products are the compounds containing the pyrrole dione which has double bond outside; When temperature is between 115-120℃,the primary products are the triscyclic compounds with benzoisoindole-dione skeleton;When temperature is between 120-130℃,the primary products are the breaken products besides getting the tricyclic products.The molecular structure of six products was determined by X-ray crystal diffraction.The possible mechanism is the intermolecular C-Pd formation,the C-H activation,the C-C Tandem cyclization.2.Palladium-catalyzed coupling cyclization of N,N-diallylacrylamide and aryl halidesThe coupling reaction of N,N-diallylacrylamide with aryl halides (R-C₆H₄X,R = H,o-CH₃,p-CH₃,p-OCH₃,p-Cl,p-CN,p-COOCH(CH₃)₂; X=I,Br)was investigated in the presence of palladium catalyst.We have found that the reactivity of the acyl group and the allyl group in the coupling reaction are equivalent,those different products are obtained through different coupling cyclization process.When the proportion of the aryl halides was changed,the aromatic products with different number substitutes could be obtained.It gives 11 new compounds.And 2 compounds of them were measured by the X-ray crystal diffraction.The possible mechanism is Heck intermolecular direct coupling and intramolecular tandem reactions.In this paper,heterocyclic complex molecules such as pyrrole diones, benzo isoindole-diones and pyrrole derivatives were gained efficiently through tandem C-C bond formations.It provided the very good method for synthesis of many natural products,formation of the complicated structure, and preparation of the matters containing optics activity and the biological activity.