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中文题名:

 可见光催化构建杂环化合物和硝基酮的研究    

姓名:

 马姗姗    

保密级别:

 公开    

论文语种:

 chi    

学科代码:

 070303    

学科专业:

 有机化学    

学生类型:

 博士    

学位:

 理学博士    

学位类型:

 学术学位    

学位年度:

 2023    

校区:

 北京校区培养    

学院:

 化学学院    

研究方向:

 有机合成方法学    

第一导师姓名:

 段新方    

第一导师单位:

 化学学院    

第二导师姓名:

 焦鹏    

提交日期:

 2023-06-25    

答辩日期:

 2023-06-12    

外文题名:

 Construction of Heterocyclic Compounds and Nitro Ketones via Visible Light Photocatalysis    

中文关键词:

 可见光催化 ; 非脱羧偶联 ; α-硝基烷基自由基 ; 硝基羟醛缩合 ; 偕溴代硝基烃 ; α ; α-二芳基烯丙醇三甲基硅醚 ; 1 ; 2-芳基迁移 ; γ-硝基酮 ; 含氮杂环 ; 碳碳偶联    

外文关键词:

 visible light photocatalysis ; nondecarboxylative coupling ; α-nitroalkyl radical ; nitro aldol condensation ; gem-bromonitroalkane ; α ; α-diaryl allyl alcohol TMS ether ; neophyl rearrangement ; γ-nitro ketone ; azacyclic compounds ; carbon-carbon coupling.    

中文摘要:

随着城市化进程的不断加快,能源短缺问题日益凸显。可见光作为绿色能源,具有可持续和环境友好的特点。如何高效利用太阳能已成为研究的焦点。利用可见光介导的有机合成反应制备功能化学品已成长为合成化学的一个重要分支。可见光催化可在温和条件下实现催化剂与底物之间的电子转移,是一种绿色、高效的反应手段。近年来,随着可见光催化的蓬勃发展,可见光介导的催化策略为杂环及其他化合物的合成提供了新的思路。本论文综述了该领域的最新研究进展,并围绕可见光催化合成杂环化合物和可见光催化脱卤偶联反应展开了相关研究工作。

1. 3-噁唑啉-5-酮是腈基叶立德的前体,是构建环亚胺或吡咯化合物极具价值的1,3-偶极子。我们通过可见光照射,促进芳基或乙烯基乙酸NHP酯、仲烷基硝基化合物和1,5,7-三氮杂二环[4.4.0]癸-5-烯之间的反应,高效合成2,2,4-三取代-3-噁唑啉-5-酮类化合物。该策略具有中等至良好的收率,广泛的底物适用范围,并首次将可见光催化拓展到NHP酯的非脱羧偶联、硝基羟醛缩合以及可见光诱导的N-氧化物脱氧,为3-噁唑啉-5-酮的合成提供了新途径。通过控制实验和Stern–Volmer磷光猝灭分析证明了自由基反应机理。DFT理论计算数据支持了我们推测的反应途径和中间体。

2. 基于卤代物在可见光下引发成自由基的催化原理,我们报道了一种温和、高效的关于偕溴代硝基烷烃与α,α-二芳基烯丙醇三甲基硅醚的偶联方法。可见光诱导生成α-硝基烷基自由基和随后的neophyl型重排组成的串联反应是实现偶联反应的关键。用TMS保护醇羟基和使用Ag2CO3捕获Br都是必要的。以中等至良好的收率制备了结构多样的α-芳基-γ-硝基酮,特别是具有1-硝基环丁基结构的γ-硝基酮。这些γ-硝基酮是合成药物相关分子的重要中间体,并且容易转化为螺环结构的硝酮和亚胺。该策略具有广泛的底物适用范围。通过控制实验和磷光猝灭实验证明了自由基反应机理。

3. 在可见光催化条件下,我们用格氏试剂实现了氮杂芳烃的烷基化和芳基化。该反应不需要任何可见光催化剂,条件温和且操作简单,收率最高达到93%,且具有较广的底物适用范围,为氮杂芳烃的烷基化和芳基化提供了新思路。

外文摘要:

With the acceleration of urbanization process, energy shortage has become increasingly prominent. Visible light as a green energy is renewable and environmentally friendly. How to use solar energy efficiently has become the focus of research. As such, visible light mediated synthesis of functional chemicals has become an important branch of synthetic chemistry. Visible light can promote electron transfer between the catalyst and the substrate under mild conditions in a green and efficient way. In recent years, with the development of visible light photocatalysis, the visible light mediated catalytic strategy provides new ideas for the synthesis of heterocyclic and other compounds. In this thesis, the latest research progress in this field was first summarized, and then we report our work on the visible light-catalyzed synthesis of heterocyclic compounds and visible light-induced dehalogenative coupling reactions.

1. 3-Oxazolin-5-ones are precursors of nitrile ylides and represent valuable 1,3-dipoles to construct cyclic imines or pyrrole compounds. We synthesized 3-oxazolin-5-ones efficiently from redox-active esters, secondary nitro compounds and 1,5,7-triazabicyclo[4.4.0]dec-5-ene under visible light irradiation. This strategy provides medium to high yields, and tolerates a wide range of substrates. For the first time, visible light photocatalysis was extended to nondecarboxylative couplings of redox-active esters, nitro aldol condensation and N-oxide deoxygenation. The new protocol paves a new way for the synthesis of 3-oxazoline-5-ones. The free radical reaction mechanism was investigated by control experiments and Stern–Volmer luminescence quenching analysis. Our hypothesized reaction pathways and intermediates were supported by DFT calculations.

2. Based on the visible light mediated radical generation from halides, a mild and efficient coupling method concerning the reactions of gem-bromonitroalkanes with α,α-diaryl allyl alcohol TMS ethers was reported. A cascade consisting of visible light induced generation of α-nitroalkyl radical and subsequent neophyl type rearrangement was key to realize the coupling reactions. TMS protection of the hydroxy group and addition of Ag2CO3 as a trapping reagent for Br are necessary. Structurally diverse α-aryl-γ-nitro ketones, especially those bearing a 1-nitrocyclobutyl structure, were prepared in moderate to high yields, which are important intermediates for a variety of pharmaceutically relevant compounds, and could be easily converted into spirocyclic nitrone and imine. This strategy tolerates a wide range of substrates. The free radical reaction mechanism was investigated by control experiments and luminescence quenching experiments.

3. Alkylation and arylation of azarenes using Grignard reagents were achieved under visible light catalysis. The reaction does not require any visible light photocatalyst, and the conditions are mild and the operations are simple. Our new protocol provides up to 93% yield, and tolerates a wide range of substrates. The new strategy provides a new idea for the alkylation and arylation of azarenes.

参考文献总数:

 79    

馆藏地:

 图书馆学位论文阅览区(主馆南区三层BC区)    

馆藏号:

 博070303/23004    

开放日期:

 2024-06-24    

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