Regioselective copper-catalyzed amination of chlorobenzoic acids: synthesis and solid-state structures of N-aryl anthranilic acid derivatives.
[reaction, structure: see text] 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 trans-anti and unprecedented trans-syn dimeric structures.
Mei
Xuefeng
X
Department of Chemistry, Georgetown University, Washington, DC 20057, USA.
August
Adam T
AT
Wolf
Christian
C
D000586:Amination; D019817:Benzoic Acid / Q000138:chemical synthesis / Q000737:chemistry*; D002384:Catalysis; D002712:Chlorides / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D019281:Dimerization; D015394:Molecular Structure; D012997:Solvents; D062367:ortho-Aminobenzoates / Q000737:chemistry*
D002712:Chlorides; D012997:Solvents; D062367:ortho-Aminobenzoates; C031385:anthranilic acid; D003300:Copper; D019817:Benzoic Acid