Cu-Catalyzed Aqueous Phase Ullmann-Type C-N Coupling Reaction Promoted by Glycosyl Ligand

A green and efficient catalytic system has been developed for the Cu-catalyzed Ullmann-type C-N coupling reactions in water.With CuI as catalyst, N-(2-hydroxyethyl)-β-D-glucopyranosylamine as ligand, aryl iodides and aryl bromides bearing various electron-withdrawing and electron-donating groups could be coupled with N-nucleophiles in water with good yields (61%～96%).The catalytic system was expanded successfully to the reaction of indoles with 4-iodoanisole in water.Keywords copper; Ullmann reaction; glycosyl ligand; water 含氮化合物是有机合成中重要的中间体, 在药物、 染料、农药的合成以及功能材料中得到了广泛应用 [1] .铜催化的 Ullmann 偶联反应, 因铜催化剂低毒低价、原 料来源简单、反应条件较温和、收率高等优点, 成为构 筑 C-N 键和合成这类含氮化合物的重要方法之一 [2] .但是, 早期的 Ullmann 偶联反应需要较高的温度(高达 200 ℃)、强碱、过量的铜源以及具有较差的官能团耐 受性.近几十年来, 配体的引入 [3] 使偶联反应更加温 和 [4] .目前, 围绕配体的设计和筛选 [5] , Ullmann 反应的 配体类型主要分为 N-N、N-O、O-O 类配体, 其中主要 的配体是马大为小组