Study On The Reactivity Of N-o-Halide Phenyl Acrylamide Via Palladium Catalyzed

Nitrogen-containing heterocyclic compounds,such as indolone,isoquinolinone,etc.,are the core skeletons of many drugs and natural products,and are widely used in synthetic chemistry,medicinal chemistry,and material chemistry.N-o-halophenylacrylamide compounds are important synthons of nitrogen-containing heterocyclic compounds.Nitrogen-containing heterocyclic compounds can be constructed simply and efficiently by palladium-catalyzed tandem reaction.In this paper,N-o-halophenylacrylamide compounds were used as substrates to construct new nitrogen-containing heterocyclic compounds including indolones and isoquinolinones by palladium catalyzed tandem reaction.It mainly includes the following parts:1.Under the condition of palladium catalysis,a method for synthesizing spirocyclic indolone derivatives was developed by using the reaction of N-o-iodophenylacrylamide and iodobenzene.This reaction firstly went through N-o-iodophenylacrylamide formed ?-alkyl Pd(II)species by Heck reaction.Secondly,intramolecular remote C-H activation formed five-membered spirocyclic palladacycle twice,which achieved coupling with one molecule of iodobenzene and insertion with one molecule of iodobenzene.This method has good regioselectivity and substrate applicability,and can provide new ideas for the synthesis of spirocyclic indolone derivatives.2.Under the condition of palladium catalysis,using N-o-iodophenylacrylamide and iodobenzene reaction,a method to form indolone spiro acenaphthene derivatives was developed.On the basis of the previous work,this method converts the benzene ring connected to alkenyl into a naphthalene ring.C2-H arylation and C8-H alkylation of naphthalene ring were realized in turn by forming five-membered and six-membered palladacycles.The reaction condition is simple and the substrate applicability is good.The indolinone spiro acenaphthylene structural unit can be obtained with ideal yield.3.Under the condition of palladium catalysis,a method of indolone derivatives with multi-functional groups was developed by using the three-component reaction of N-o-iodophenylacrylamide,morpholine 4-benzoate and acrylate.This method achieves alkenylation and benzoyloxylation of spirocyclic palladacycle.It is worth mentioning that in this reaction,morpholine 4-benzoate was found to provide an oxygen source rather than a nitrogen source.4.Under the condition of palladium catalysis,the synthesis method of indolone spiro-indoline derivatives with all-carbon tetrasubstituted olefin structure was developed by using the reaction of o-iodoarylacrylamide with eneyne and arylphenylboronic acid.In this process,N-o-iodophenylacrylamide introduces an acetylene bond and undergoes a Heck reaction to form a ?-alkyl Pd(II)species,then forms an alkenyl palladium intermediate through chemical selectivity,which is then captured by phenylboronic acid.This reaction has simple condition,good regioselectivity and wide applicability of substrates,and can obtain indolone spiro-indoline derivatives with all-carbon tetrasubstituted olefin structure with ideal yield.5.Under the condition of palladium catalysis,a method for synthesizing fused dibenzisoquinoline dione and dibenzisoquinoline ketones was developed by using the reaction of acrylamide aryl iodide with o-bromobenzoic acid.In this process,the acrylamide aryl iodide undergoes Heck reaction under palladium catalysis to form ?-alkyl Pd(II)species,realizes the fused palladacycles formed by the activation of ortho C-H bond of C-I bond and decarboxylation coupling insertion via o-bromobenzoic acid,synthesizes the fused dibenzisoquinoline dione and dibenzisoquinoline compounds in good yield.This reaction has good substrate applicability and functional group tolerance,the substrate substituted with an aryl group on the alkenyl group can also exhibit good regioselectivity.