Intramolecular Nucleophilic Addition Of Aryl-halides To ?-ketoamides And ?-iminoamides:Synthetic Access To Oxindole

3,3'-disubstituted oxindole substructure exists widely in natural products and drugs.The development of novel synthetic methods has attracted much attention from organic chemists.The transition-metal catalyzed intramolecular cyclization of aryl amides to construct oxindole has been a extensively studied access,featuring high efficiency and short synthetic route.The thesis mainly studies the intramolecular nucleophilic addition of aryl halides to ?-ketoamides and a-iminoamide to synthes ize 3,3'-disubstituted oxindole in the presence of nickel catalyst.1.With N-(2-bromophenyl)-N-methyl-2-oxo-arylamide as the substrate,under the optimal reaction conditions of(Ni(acac)2(5 mol%)as a catalyst,chiral spiro phosphor-amidite(L15)(6 mol%)as a ligand,ZnMe2(0.1 M,2 eq.)as reducing agent and THF as solvent at 50 C),a series of 3-hydroxyoxindole derivates were obtained with high yields(up to 89%)and in moderate enantioselectivities(up to 66%).2.With N-(2-bromophenyl)-N-methyl-2-imino-arylamide as the substrate,under the o optimal conditions of(Ni(dppe)Br2(5 mol%)as a catalyst,Zn powder(2.5 eq.)as reducing agent in CH3CN at 70 0C),a series of 3-aminooxindole derivates were obtained with good to excellent yield(up to 95%).