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Paper | Special issue | Vol 97, No. 1, 2018, pp.451-458
Published online, 13th April, 2018
DOI: 10.3987/COM-18-S(T)34
Computational Study for the Selective Aromatic Nucleophilic Substitution on 4-Dimethylamino-2-methoxy-3-trifluoroacetylquinoline

Norio Ota, Shota Sasakawa, Yasuhiro Kamitori, and Etsuji Okada*

*Department of Chemical Science and Engineering, Graduate School of Engineering, Kobe University, 1-1 Rokkodai-cho, Nada-ku, Kobe 657-8501, Japan


The selective nucleophilic substitution on aromatic ring occurs at the 4-position of 4-dimethylamino-2-methoxy-3-trifluoroacetylquinoline 1 by the reaction with various amines to afford the N-N exchanged products solely, and any O-N exchange reactions at the 2-position are not performed. Our DFT calculation study led to a rational explanation of this unique selectivity based on the frontier electron densities (LUMO) of 1 and energies of the Meisenheimer complexes which were assumed to be formed as the intermediates on such substitution course. It was also investigated about the reaction of related 4-dimethylamino-2-methoxyquinolines bearing various electron-withdrawing groups at the 3-position.