Benzamide Radical Addition/cyclization Synthesis Several Isoquinolinediones

Nitrogen-containing heterocycle isoquinolinediones are important molecular,which widely exist in natural products and have important biological properties.They are widely used in agricultural chemistry and medicinal chemistry.The development of synthetic methods is one of the hot field in synthetic chemistry.Recently,many organic chemists have showed increasing interest on the synthetic methodologies of isoquinolinediones using by cheap metal(such as copper,iron)or by photocatalysis.Based on related research reports and our previous work,this thesis developed several low-cost copper-catalyzed or visible-light-induced,cascade radical cyclization of N-alkyl-N-methacryloylbenzamide toward isoquinolinodiones and its derivatives.The specific research content is as follows:Firstly,in this work,copper/air catalysed the radical cyclization of alkenes with alkyl azo reagents to synthesize 7-tert alkyl isoquinolinodiones was developed.In this reaction,the alkyl radicals produced by the alkyl azo reagent were used as the coupling partner,and successfully realized the benzamides cascadse Heck-type insertion alkenes / cyclization / carbon(tertiary)-carbon bond formation,and meta-selectively lead to a series of isoquinoline-1,3(2H,4H)dione.The reaction has wide scope and easy-handling and the starting material is inexpensive and commercial available.Followed by the same substrate,a copper-catalyzed cyclization reaction of N-acryloylbenzamide with azo compounds was developed.CuI as catalyst,air as oxidant,K3PO4 as base and DMF as solvent and in 90 oC.A series of isoquinolinedione containing α-cyano quaternary carbon center were selectively prepared using alkyl azo reagent as free radical,In addition,we developed a method to synthesize polyfluoroisoquinolinedione by visible light-induced radical cascade cyclization of N-alkyl-N-methacryloylbenzamide.Under visible light irradiation,N-alkyl-N-methacryloylbenzamide undergoes tandem free radical cyclization with perfluorinated iodoalkanes.A series of potentially biological active compounds perfluorinated affording isoquinolinediones were synthesized in 54% to 80% yields.