Rhodium(II) Acetate and Nafion-H Catalyzed Decomposition of N-Aryldiazoamides. An Efficient Synthesis of 2(3H)-Indolinones

Article abstract of DOI:10.1021/jo00240a015

N-Aryldiazoamides undergo facile intramolecular aromatic substitution to form 2(3H)-indolinones in high yield when these reactions are performed in the presence of a catalytic amount of rhodium(II) acetate.Diazoacetamides react smoothly at room temperature in dichloromethane, whereas the corresponding less reactive diazoacetoacetamides respond in the refluxing benzene.A meta methoxy substituent directs substitution solely to its para position, but a meta methyl substituent offers virtually no selectivity for substitution.N-α-Naphtyldiazoacetamide undergoes exclusive intr amolecular substitution at the β-position.The perfluororesinsulfonic acid Nafion-H also catalyzes the decomposition of N-aryldiazoacetamides, but not N-aryldiazoacetamides, and yields of 2-idolinones are even greater than those obtained with rhodium carboxylate catalysis even though higher reaction temperatures are required to initiate decomposition