大学化学 >> 2022, Vol. 37 >> Issue (5): 2111090.doi: 10.3866/PKU.DXHX202111090

所属专题: 第2届全国大学生化学实验创新设计竞赛

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可见光促进的香豆素类衍生物的绿色仿生催化合成及分光光度法定量分析

张帝, 夏天, 罗永祥, 王兮()   

  • 收稿日期:2021-11-30 录用日期:2021-12-07 发布日期:2022-04-11
  • 通讯作者: 王兮 E-mail:cccewangxi@hnu.edu.cn
  • 作者简介:王兮,Email: cccewangxi@hnu.edu.cn
  • 基金资助:
    湖南大学教育教学改革项目

Visible-Light-Driven Biomimetic Catalytic Green Synthesis and Quantitative Analysis of Coumarin Derivatives Based on Spectrophotometry

Di Zhang, Tian Xia, Yongxiang Luo, Xi Wang()   

  • Received:2021-11-30 Accepted:2021-12-07 Published:2022-04-11
  • Contact: Xi Wang E-mail:cccewangxi@hnu.edu.cn

摘要:

香豆素结构广泛存在于各种功能分子中,人们在香豆素衍生物的合成中已经取得一些显著进展,但这些方法还存在一定的局限性,如反应条件苛刻、环境不友好等。本实验方案采用了前沿的合成方法,从半微量反应、连续流动相合成、光反应、仿生催化、绿色化学、自由基过程、计算化学等多维度丰富了本科有机实验教学内容。此外,在加深本科生对有机化学基础知识的理解和实验技能的掌握以及对有机化学的兴趣培养方面,都具有非常积极的作用。多学科交叉的思维模式也有很好的教学意义。

关键词: 可见光促进, 仿生催化, 氧气氧化, 烯烃的E/Z构型异构, 自由基环化

Abstract:

Coumarin structures are commonly found in many functional molecules. Although conspicuous progress has been made to synthesize coumarin derivatives, these approaches are often limited by harsh reaction conditions, low functional group tolerances, and environmentally harmful processes. The frontier synthesis method has been applied in this experimental design. The coumarin framework was accessed through two steps in the one-pot approach: EZ isomerization of cinnamic acid visible-light and subsequent C(sp2)-H oxidative cyclization, using vitamin B2 as the photocatalyst. The reaction was characterized by mild conditions, inexpensive starting materials and reagents, atom economy, and environmentally friendly processes. The reaction was conducted in large-scale by using a customized continuous flow device based on the photocatalyzed gaseous reaction. This experimental design augments organic experimental teaching of semi-micro-scale reactions, continuous flow synthesis, photoreactions, biomimetic catalysis, green chemistry, radical processes, and computational chemistry. In addition, it also plays an important role in helping undergraduate students to gain in-depth understanding of basic organic chemistry, master experimental skills, and develop an interest in organic chemistry. Finally, a spectrophotometric method for quantitative analysis of various coumarin derivatives was also explored based on the chromogenic reactions of metal complexes. It is easy to popularize this teaching model for multi-disciplinary experiments.

Key words: Visible-light-driven, Biomimetic catalysis, Oxygen oxidation, E/Z isomerization of olefins, Radical cyclization

MSC2000: 

  • G64