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Regioselective Copper-Catalyzed Amination of Chlorobenzoic Acids:  Synthesis and Solid-State Structures of N-Aryl Anthranilic Acid Derivatives

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posted on 06.01.2006, 00:00 by Xuefeng Mei, Adam T. August, Christian Wolf
A chemo- and regioselective copper-catalyzed cross-coupling reaction for effective amination of 2-chlorobenzoic acids with aniline derivatives has been developed. The method eliminates the need for acid protection and produces a wide range of N-aryl anthranilic acid derivatives in up to 99% yield. The amination was found to proceed with both electron-rich and electron-deficient aryl chlorides and anilines and also utilizes sterically hindered anilines such as 2,6-dimethylaniline and 2-tert-butylaniline. The conformational isomerism of appropriately substituted N-aryl anthranilic acids has been investigated in the solid state. Crystallographic analysis of seven anthranilic acid derivatives showed formation of two distinct supramolecular architectures exhibiting transanti and unprecedented transsyn dimeric structures.