Palladium-catalyzed Domino Reaction Of Halides With Dienes Of Containing Active Acryl Group

Transition metal Pd-catalyzed cyclization is a versatile method for the construction of ring systems.In this thesis,we have explored the cycli coupling reaction of dienes with a series of halides catalyzed by palladium.1.Palladium-Catalyzed Cyclization Reaction of Aryl halides With N-allyl-N-benzylacrylamide.Reactions of N-allyl-N-benzylacrylamide with substituted aryl halides (R-C₆H₄X,R = H,Cl,o-CH₃,p-CH₃,p-OCH₃,p-Cl,m-Cl,p-CN,p-CHO, p-COOCH₂CH₃;X=Cl,Br)in the presence of palladium acetate have been studied.It affords eleven dihydropyrrolone derivatives.The reactions gave the expected cyclic coupling products in moderate yield. All the compounds have been characterized by IR,MS,EA and NMR spectroscopy.Three compounds structure have been determined by X-ray single crystal analysis.To explain the formation of dihydropyrrolone derivatives,we proposed the response mechanism.2.Palladium-Catalyzed Cyclization Reaction Of Aryl halides With N -benzyl-(cyclohex-2-enyl)acrylamide.Reactions of N-benzyl-(cyclohex-2-enyl)acrylamide with substituted aryl halides(R-C₆H₄X,R = H,Cl,o-CH₃,p-CH₃,p-OCH₃,p-Cl,m-Cl p-CN,p-CHO,p-COOCH₂CH₃;X=C1,Br)in the presence of palladium acetate have been studied.The research indicated that the reaction tempe-rature has the tremendous influence to this reaction When temperature is about120℃,we can't obtain the expected compound.When temperature is about140℃,we obtained 11 four links in the together heterocyclic co-mpound.Product4-benzyl-5-oxo-l,2,3,3a,4,5,5a,6,9,10b-decahydronaphtho[3,2,1-cd] indole-9-carbonitr crystal structure indicated that,this response involved the benzene ring carbon hydrogen activation.The structure of two compounds has been determined by X-ray single crystal analysis.3.Palladium-Catalyzed Cyclization Reaction Of Aryl halides With N-allyl-N-(cyclohex-2-enyl)acrylamideReactions of N-allyl-N-(cyclohex-2-enyl)acrylamide with substituted aryl halides(R-C₆H₄X,R = H,,p-CH₃,p-CHO:X= Br)in the presence of palladium acetate have been studied.It affords three dihydropyrrolone derivatives.The research indicated that,under the same condition, reaction occurs on allyl group rather than cyclohexene group.Thus,this reaction is a selectivechemistry,namely,first response is befelled in the small sterically hindered group.4.Palladium-Catalyzed Cyclization Reaction Of 3-bromoprop-1-ene with 1,6-dienes.Reaction of N-allyl-N-(cyclohex-2-enyl)acrylamide or N-allyl-N-Benzylacrylamide or N -benzyl-(cyclohex-2-enyl)acrylamide with 3-bromoprop-1-ene in the presence of palladium acetate has been studied. It affords two dihydropyrrolone derivatives.Here,aryl halides are replaced by 3-bromoprop-1-ene;this is a breakthrough to this system.