化学学报 ›› 2014, Vol. 72 ›› Issue (11): 1139-1143.DOI: 10.6023/A14080584 上一篇    下一篇

研究通讯

铜催化脒类化合物苄位sp3C—H键胺化反应:合成喹唑啉衍生物

张茜, 吕允贺, 李燕, 熊涛, 张前   

  1. 东北师范大学化学学院 长春市 130024
  • 投稿日期:2014-08-14 发布日期:2014-10-10
  • 通讯作者: 张前 E-mail:Zhangq651@nenu.edu.cn
  • 基金资助:

    项目受国家自然科学基金(Nos. 21172033, 21372041)及高等学校博士点基金(No. 20110043110002)资助.

Copper-Catalyzed Benzylic sp3 C-H Amination Reaction of Amidines: Synthesis of Quinazoline Derivatives

Zhang Qian, Lü Yunhe, Li Yan, Xiong Tao, Zhang Qian   

  1. Department of Chemistry, Northeast Normal University, Changchun 130024
  • Received:2014-08-14 Published:2014-10-10
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21172033, 21372041) and the Specialized Research Fund for the Doctoral Program of Higher Education (No. 20110043110002).

报道了N-芳基脒类化合物苄位sp3 C—H键的分子内直接胺化反应, 以42%~82%的收率成功合成了一系列多取代的喹唑啉衍生物, 并初步研究了该反应的机理.

关键词: 铜, N-芳基脒, C—N键形成, 喹唑啉衍生物

Quinazoline motif is an important heterocyclic framework, which widely exists in many biologically active molecules and natural products. Although numerous synthetic efforts have been made for the preparation of quinazoline derivatives in recent years, it is still highly desirable to search for a more convenient and efficient approach. As part of our ongoing interest in transition-metal-catalyzed C—H functionalization, herein, we report a novel copper-catalyzed synthesis of quinazoline derivatives from amidines. During these transformations, the selectivity of benzylic sp3 C—H over aryl sp2 C—H bond was efficiently realized. Various 2-arylquinazoline derivatives were obtained in moderate to good yields. A representative procedure for the copper-catalyzed construction of quinazolines from amidines is as following: N-(o-tolyl)benzimidamide (1a, 0.4 mmol, 89.7 mg), Cu(OTf)2 (0.04 mmol, 13.8 mg) and Ag2CO3 (0.8 mmol, 219 mg) were added to a 25 mL sealed tube, followed by addition of DMF (2 mL). The mixture was stirred at 140 ℃ for 10 h. After cooling to room temperature, the mixture was poured into ice-water and extracted with CH2Cl2 (15 mL×3). The combined organic layers were dried (Na2SO4), filtered over Celite, evaporated in vacuo. The residue was purified by a shot flash silica gel column chromatography (petroleum ether/ethyl acetate, V:V=15:1) to afford the product 2a (71%, 62.4 mg).

Key words: copper, N-arylamidines, C—N bond formation, quinazoline derivatives