有机化学 ›› 2014, Vol. 34 ›› Issue (11): 2304-2308.DOI: 10.6023/cjoc201405026 上一篇    下一篇

研究论文

环钯化苯基咪唑啉-卡宾络合物的合成及催化Suzuki反应研究

赵雪梅, 肖志强, 梁婷, 高翔, 郝新奇, 宋毛平   

  1. 郑州大学化学与分子工程学院 河南省化学生物与有机化学重点实验室 郑州 450001
  • 收稿日期:2014-05-17 修回日期:2014-06-16 出版日期:2014-11-25 发布日期:2014-07-02
  • 通讯作者: 郝新奇,xqhao@zzu.edu.cn;宋毛平,mpsong@zzu.edu.cn E-mail:xqhao@zzu.edu.cn;mpsong@zzu.edu.cn
  • 基金资助:

    国家自然科学基金(Nos.21102135, 21272217, J1210060)资助项目.

Synthesis of Cyclopalladated Phenyl Imidazoline-Carbene Complexes and Catalytic Study in Suzuki Reaction

Zhao Xuemei, Xiao Zhiqiang, Liang Ting, Gao Xiang, Hao Xinqi, Song Maoping   

  1. College of Chemistry and Molecular Engineering, Henan Key Laboratory of Chemical Biology and Organic Chemistry, Zhengzhou University, Zhengzhou 450001
  • Received:2014-05-17 Revised:2014-06-16 Online:2014-11-25 Published:2014-07-02
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos.21102135, 21272217, J1210060).

以间硝基苯甲酸或苯甲酸和(S)-缬氨醇为起始原料, 室温反应制得酰氨基醇1a1b, 在亚硫酰氯存在下, 酰胺基醇与对甲苯胺关环反应得到苯基咪唑啉化合物2a2b. 通过对苯基咪唑啉配体2进行钯化反应、1,3-二苄基苯并咪唑盐解聚, 得目标产物环钯化苯基咪唑啉-卡宾络合物3a3b. 通过1H NMR, 13C NMR, IR, MS和元素分析等手段对新化合物3a3b进行了表征. 进一步通过单晶X射线衍射对3a进行了结构确证, 络合物3a晶体结构表明该化合物通过分子间氢键形成一维链状结构. 催化性能考察发现, 络合物3a在萘硼酸和碘代甲氧基萘的Suzuki偶联反应中表现出较好的催化活性.

关键词: 环钯, 苯基咪唑啉, 卡宾络合物, 晶体结构, Suzuki

The amido alcohols compounds 1a and 1b were synthesized from commercially available 3-nitrobenzoic acid or benzoic acid and (S)-2-amino-3-methyl-1-butanol at room temperature. The amido alcohols, when treated with excess thionyl chloride, followed by p-toluidine, gave the phenyl imidazoline compounds 2a and 2b. Cyclopalladated phenyl imidazoline-carbene complexes 3a and 3b were obtained by the reaction of phenyl imidazolines 2a and 2b with Pd(OAc)2/LiCl followed by treatment with 1,3-dibenzyl-benzimidazolium chloride. All the complexes 3a and 3b were characterized by 1H NMR, 13C NMR, MS and elemental analysis. In the crystal of complex 3a, the compound was assembled to a chain supramolecular structure by the intermolecular hydrogen bonds. And complex 3a presented good catalytic effect on Suzuki reaction.

Key words: cyclopalladated, phenyl imidazoline, carbene complex, crystal structure, Suzuki