Organocatalytic Regio- and Asymmetric <i>C</i>-Selective S_NAr ReactionsStereoselective Synthesis of Optically Active Spiro-pyrrolidone-3,3‘-oxoindoles

The first example of catalytic enantioselective nucleophilic aromatic substitution of β-dicarbonyl compounds is presented. An <i>O</i>-benzoylated cinchona alkaloid derivative catalyst gave a selective <i>C</i>-arylation reaction compared to, e.g., the corresponding benzylated catalyst which provided a 1:1 mixture of the <i>C</i>- and <i>O</i>-arylation products. The reaction proceeds well for various aromatic compounds with different 1,3-dicarbonyl compounds, and the optically active products are obtained in very high yields and with up to 92% ee. One further scope of the organocatalytic enantioselective nucleophilic aromatic substitution reaction is demonstrated by the synthesis of the optically active spiro-pyrrolidone-3,3‘-oxoindole structure.