有机化学 ›› 2017, Vol. 37 ›› Issue (8): 2094-2100.DOI: 10.6023/cjoc201701044 上一篇    下一篇

研究论文

手性双苯并噁嗪-2-酮二酚衍生物的高效合成及其在不对称催化中的应用

林伟a, 蔡琦a, 郑纯智a, 黄志斌b, 史达清b   

  1. a 江苏理工学院化学与环境工程学院 常州 213001;
    b 苏州大学材料与化学化工学部 苏州 215123
  • 收稿日期:2017-01-22 修回日期:2017-03-14 出版日期:2017-08-25 发布日期:2017-04-10
  • 通讯作者: 林伟, 史达清 E-mail:linwei@jsut.edu.cn;dqshi@suda.edu.cn
  • 基金资助:

    国家自然科学基金(No.21502074)和江苏省高校自然科学重大研究(No.15KJA150006)资助项目.

Efficient and Stereoselective Synthesis of the Chiral Dihydroxy-bisquinazoline-dione Derivatives and Their Application in Asymmetric Catalysis

Lin Weia, Cai Qia, Zheng Chunzhia, Huang Zhibinb, Shi Daqingb   

  1. a School of Chemistry and Environmental Engineering, Jiangsu Technology of University, Changzhou 213001;
    b College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123
  • Received:2017-01-22 Revised:2017-03-14 Online:2017-08-25 Published:2017-04-10
  • Contact: 10.6023/cjoc201701044 E-mail:linwei@jsut.edu.cn;dqshi@suda.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21502074) and the Major Basic Research Project of the Natural Science Foundation of the Jiangsu Higher Education Institutions (No. 15KJA150006).

探索了手性苯并噁嗪-2-酮二酚衍生物的高效合成,以甲氧基取代的2-羟基苯甲醛衍生物和手性环己二胺为起始原料合成手性双亚胺,后经低价钛促进下还原、偶联与固体光气作用,构建了含有甲氧基的手性苯并噁嗪-2-酮衍生物,通过官能团转化,利用三溴化硼还原得到相应的手性苯并噁嗪-2-酮二酚衍生物.在此基础上,考察了手性苯并噁嗪-2-酮二酚催化剂在醛与二乙基锌不对称加成中的应用.此方法为合成手性苯并噁嗪-2-酮二酚衍生物提供了一条有效途径.

关键词: 双苯并噁嗪-2-酮, 不对称, 合成

An efficient and simple method for the synthesis of chiral benzo[5,6][1,3]oxazino[4,3-c]quinoxaline-dione is reported. 2-Hydroxybenzaldehydes and diamines were utilized as the starting materials, the formed diimines then underwent a reductive-cyclization process with triphosgene to give bis-quinazoline-dione derivatives induced by low-valent titanium reagent. Then through the conversion of functional groups, the bis-quinazoline-dione compounds containing hydroxy group have been obtained from their corresponding compounds containing methoxy group in the presence of BBr3. In addition, the dihydroxy-bis-quinazoline-dione derivatives were applied on the asymmetric nucleophilic addition of Et2Zn to aldehydes. The reported method is the efficient approach for the synthesis of dihydroxy-bis-quinazoline-dione derivatives.

Key words: bis-quinazoline-dione, asymmetric, synthesis