Study On Synthesis Of 2,2-bis(4-aminoaryl)-2-(4-pyranone) Acetate And Furyl Oxime

Two aspects were mainly researched in this paper.Initially,Ag?I?/Rh?II?-mediatedtandemreactionforthe synthesis of 2,2-bis?4-aminoaryl?-2-?4-pyranonyl?acetates via2-diazo-3,5-dioxo-6-ynoate?ynones?and aromatic amines have been studied.Then,nitromethane and ene-yne-ketones were employed as materials to synthesize nitromethylfuran derivatives in the presence of Cu?I?and Lewis base,and nitromethylfuran derivatives further were transformed into bispolysubstituted furanyl oxime derivatives.These contents were discussed in three parts in this paper.A review of the literatures on the reactions of X-H insertion of diazo compounds,C?sp³?/C?sp²?-H activation,polysubstituted furan and nitro compounds were shown in chapter one.In the second chapter,we have realized the reaction of diazo compounds with one or two equivalent of N,N-disubstitutedaniline?N-substitutedindole?to selectively synthesize 2-?4-aminoaryl?-2-?4-pyranonyl?acetates and2,2-bis?4-aminoaryl?-2-?4-pyranonyl?acetates for the first time.Theoptimalconditionsfortheformationof2,2-bis?4-aminoaryl?-2-?4-pyranonyl?acetates were obtained as follows:the utilization of AgSbF₆?10 mol%?/Rh₂?OAc?₄?10 mol%?/Ag₃PO₄?60mol%?as catalyst,DCE as solvent at 25 ^oC under air.For most of aromatic amines,target products were obtained in 55%-74%yield.Electron-rich aromatic amines possess the higher reactivity.On the basis of this strategy,synthesis of asymmetry aromatic amines,which is a challenge task in synthetic chemistry,has been achived.In the third chapter,the synthesis of polysubstituted nitromethylfurans was explored based on Cu?I?/DBU-mediated tandem reaction of ene-yne-ketones with nitromethane as substrates.Subsequently,nitromethylfurans were employed to further synthetic application to obtain furyl oxime derivatives.A series of furyl oxime derivatives were synthesized in 24%-65%yield.The optimal conditions for the formation of bispolysubstituted furyl oxime were obtained as follows:CuI?20 mol%?and DBU?50 mol%?as the catalyst,anhydrous THF as the solvent at 60 ^oC under nitrogen atmosphere.This protocol afforded highly functionalization furyl oxime from available materials,providing a novel strategy for the formation of complicated furan compound.