金属催化C-N键形成.pdfVIP

Amino Acid Promoted CuI-Catalyzed C N Bond Formation between Aryl Halides and Amines or N-Containing Heterocycles Hui Zhang,† Qian Cai,‡ and Dawei Ma*,‡ Department of Chemistry, Fudan University, Shanghai 200433, China, and State Key Laboratory of Bioorganic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, China madw@mail.sioc.ac.cn Received March 8, 2005 CuI-catalyzed coupling reaction of electron-deficient aryl iodides with aliphatic primary amines occurs at 40 °C under the promotion of N-methylglycine. Using L-proline as the promoter, coupling reaction of aryl iodides or aryl bromides with aliphatic primary amines, aliphatic cyclic secondary amines, or electron-rich primary arylamines proceeds at 6090 °C; an intramolecular coupling reaction between aryl chloride and primary amine moieties gives indoline at 70 °C; coupling reaction of aryl iodides with indole, pyrrole, carbazole, imidazole, or pyrazole can be carried out at 7590 °C; and coupling reaction of electron-deficient aryl bromides with imidazole or pyrazole occurs at 6090 °C to provide the corresponding N-aryl products in good to excellent yields. In addition, N ,N-dimethylglycine promotes the coupling reaction of electron-rich aryl bromides with imidazole or pyrazole to afford the corresponding N-aryl imidazoles or pyrazoles at 110 °C. The possible action of amino acids in these coupling reactions is discussed. Introduction