有机化学 ›› 2018, Vol. 38 ›› Issue (1): 1-10.DOI: 10.6023/cjoc201708050 上一篇    下一篇

所属专题: 庆祝吴养洁院士九十华诞专辑

综述与进展

苯胺催化在生物大分子修饰和材料合成中的应用

蔡茂a,b, 韩彦方a,b, 章琪a,b, 罗三中a,b   

  1. a 中国科学院化学研究所 分子识别与功能重点实验室 北京 100190;
    b 中国科学院大学 北京 100049
  • 收稿日期:2017-08-23 修回日期:2017-09-28 发布日期:2017-10-11
  • 通讯作者: 罗三中 E-mail:luosz@iccas.ac.cn
  • 基金资助:

    国家自然科学基金(Nos.21332002,21561162001)和中央高校基本科研业务费专项资金(No.20720150046)资助项目.

Aniline Catalysis in Bioconjugations and Material Synthesis

Cai Maoa,b, Han Yanfanga,b, Zhang Qia,b, Luo Sanzhonga,b   

  1. a Key Laboratory for Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190;
    b University of Chinese Academy of Sciences, Beijing 100049
  • Received:2017-08-23 Revised:2017-09-28 Published:2017-10-11
  • Contact: 10.6023/cjoc201708050 E-mail:luosz@iccas.ac.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21332002, 21561162001) and the Fundamental Research Funds for the Central Universities (No. 20720150046).

成肟或成腙的经典缩合反应具有较高的化学选择性,且底物易于合成,是一类简单但又重要的偶联反应,在生物分子修饰和材料合成中具有重要的应用价值.但该反应十分缓慢,而且往往需要在酸性溶液以及较高的底物浓度下进行,限制了其广泛应用.近年来的研究表明,苯胺作为亲核性催化剂可以显著加速成肟和成腙等缩合反应,初步解决了这类反应的速率问题,反应条件更为温和,生物兼容性好,已成为目前生物大分子修饰中最通用的偶联手段.本文详述了近年来芳胺催化剂的设计与发展、芳胺催化机制和构效关系以及高活性芳胺催化剂在生物大分子修饰和材料合成中的应用,并对未来的发展做了展望.

关键词: 肟, 腙, 苯胺催化, 大分子修饰, 材料合成

The oxime or hydrazone formation is a classic condensation reaction between aldehydes/ketones and hydroxyl amine or hydrazine. It is a simple, yet fundamental coupling reaction that has been widely applied in the ligations and conjugations of biomolecules and material synthesis. However, the reactions are usually sluggish and normally require acidic conditions with large excess of substrates to facilitate conversion, which limit their wide applications. Recent studies have shown that aniline as a nucleophilic catalyst can significantly accelerate the oxime/hydrazone formation reaction, preliminarily solving the reaction rate issue under mild and bio-compatible conditions. Therefore, it has been the most common coupling method in the modification of biological macromolecules. In this review, the design and development of aromatic amine catalyst in recent years as well as the catalytic mechanism and structure activity relationship are summarized. The application of highly active aniline catalysis in bioconjugations and material synthesis was also included together with a prospect for future development.

Key words: oxime, hydrazone, aniline catalysis, bioconjugation, material synthesis