Study On The Synthesis Of Indolones

Indolinone building blocks are widely found in natural products and pharmaceutical active molecules,which exhibit superior biological activities[1].In this paper,a series of potentially biologically active dispiro[indoline-3,3’-furan-2’,3,"-pyrrolidines]derivatives,polycyclic spirooxindoles derivatives,dihydroindolo[3,2-c]phenothiazines derivatives,spiro[indoline-3,4’-pyrrolo[3,4-b]pyridine]derivatives and spiro[bispyrro[3,4-b:3’,4’e]pyridine-8,3’-indoline]one derivatives.Under room temperature,ethyl acetate as solvent,DABCO（1,4-diazabicyclo[2.2.2]octane）and potassium carbonate as base,the[3+2]cycloaddition reaction of MBH maleimides of isatins with 1,3-dicarbonyl compound afforded 26 functionalized dispiro[indoline-3,3’-furan-2’,3"-pyrrolidines]derivatives in higher yields and with high diastereoselectivty.However,the similar reaction of MBH adducts of isatins derived from acrylonitrile and methyl acrylate resulted in 4 functionalized spiro[indoline-3,4’-pyranes]derivatives in good yields through formal[3+3]cycloaddition reaction.1,3-Indandione showed different reactivity with other cyclic 1,3-dicarbonyl compounds,resulting in 4 chainlike compounds.The structures of the synthesized compounds were characterized by 1H NMR、13C NMR、HRMS、IR,etc.,and the single crystal molecular structure of 6 compounds was determined by single crystal diffraction.The acetic acid promoted reaction of 3-hydroxy-3-（indol-3-yl）indolin-2-ones and 2（benzo[b][1,4]thiazine-3-methylene）acetate showed molecular diversity.The reaction in ethanol at room temperature in the presence of acetic acid resulted in 12 3,3-disubstituted oxindoles derivatives in high yields.Under high temperature conditions,the reaction with 3hydroxy-3-（indol-3-yl）indolin-2-ones with N-alkyl groups gave 14 polycyclic spirooxindoles derivatives in satisfactory yields.However,a similar reaction with 3-hydroxy-3-（indol-3yl）indolin-2-ones with NH groups afforded 9 dihydroindolo[3,2-c]phenothiazines derivatives.The structures of the synthesized compounds were characterized by 1H NMR、13C NMR、HRMS、IR,etc.,and the single crystal structure of 6 of them was determined.The[3+3]cycloaddition of MBH maleimides of isatins with 1-methyl-3-（phenylamino）1H-pyrrole-2,5-dione was studied at room temperature with DABCO as base and acetonitrile as solvent reaction.MBH maleimides of isatins with different structures exhibit different diastereoselectivities.The structures of the synthesized 36 spiro[indoline-3,4’-pyrrolo[3,4b]pyridine]derivatives and 14 spiro[bispyrro[3,4-b:3’,4’-e]pyridine-8,3’-indoline]one derivatives were characterized by 1H NMR、13C NMR、HRMS、IR,etc.,and the single crystal structure of 5 of them was determined.