Zhang Hui, Cai Qian, Ma Dawei
Department of Chemistry, Fudan University, Shanghai 200433, China.
J Org Chem. 2005 Jun 24;70(13):5164-73. doi: 10.1021/jo0504464.
CuI-catalyzed coupling reaction of electron-deficient aryl iodides with aliphatic primary amines occurs at 40 degrees 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 60-90 degrees C; an intramolecular coupling reaction between aryl chloride and primary amine moieties gives indoline at 70 degrees C; coupling reaction of aryl iodides with indole, pyrrole, carbazole, imidazole, or pyrazole can be carried out at 75-90 degrees C; and coupling reaction of electron-deficient aryl bromides with imidazole or pyrazole occurs at 60-90 degrees 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 degrees C. The possible action of amino acids in these coupling reactions is discussed.
在N-甲基甘氨酸的促进作用下，缺电子芳基碘化物与脂肪族伯胺的CuI催化偶联反应在40℃下进行。以L-脯氨酸作为促进剂，芳基碘化物或芳基溴化物与脂肪族伯胺、脂肪族环状仲胺或富电子芳基伯胺的偶联反应在60 - 90℃下进行；芳基氯与伯胺部分之间的分子内偶联反应在70℃下生成吲哚啉；芳基碘化物与吲哚、吡咯、咔唑、咪唑或吡唑的偶联反应可在75 - 90℃下进行；缺电子芳基溴化物与咪唑或吡唑的偶联反应在60 - 90℃下进行，以良好至优异的产率提供相应的N-芳基产物。此外，N,N-二甲基甘氨酸促进富电子芳基溴化物与咪唑或吡唑的偶联反应，在110℃下得到相应的N-芳基咪唑或吡唑。讨论了氨基酸在这些偶联反应中的可能作用。
