Copper(II)-Mediated Oxidative Coupling of 2-Aminonaphthalene Homologues. Competition between the Straight Dimerization and the Formation of Carbazoles

• Published in: Journal of organic chemistry Vol. 66; no. 4; pp. 1359 - 1365
• Main Authors: Vyskočil, Štěpán, Smrčina, Martin, Lorenc, Miroslav, Tišlerová, Iva, Brooks, Robin D, Kulagowski, Janusz J, Langer, Vratislav, Farrugia, Louis J, Kočovský, Pavel
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 23-02-2001
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo005691w

Whereas the Cu(II)-mediated oxidative coupling of 2-aminonaphthalenes 7a and 7b results in the clean formation of 1,1‘-binaphthyls 13a and 13b, respectively, their higher homologues and congeners 8−12 have been found to exhibit a different reaction pattern. Thus, 2-aminoanthracene (8) gave a ∼1:1 mixture of the expected bianthryl derivative 15 and the carbazole 16, whereas the 9-aminophenanthrene (10), 3-phenyl-1-aminonaphthalene (11), and 2-aminochrysene (12) produced almost exclusively the corresponding carbazoles 19, 20, and 21, respectively. By contrast, the isomeric 3-aminophenanthrene (9) gave rise to the azo compound 17 as a result of the preferential oxidation on the nitrogen. The carbazoles have been shown to arise directly from the coupling reactions rather than from the primarily formed binaphthyls. Alternatively, carbazole 19 can also be prepared from 1b on reaction with hydrazine. On the other hand, treatment of 3a with hydrazine resulted in the formation of a ∼2:7 mixture of amine 11 and arylhydrazine 22. 2,2‘-Diamino-1,1‘-bianthryl (15) has been resolved into enantiomers via cocrystallization with (−)-N-benzylcinchonidinium chloride and shown to have (R)-(−)-15 configuration by X-ray crystallography.