有机硫化合物广泛存在于药物化学、生物化学、有机合成和材料科学领域中。尤其是有机硫化物中的砜类化合物和含硫亚胺类物质在药物中有着很好的应用。因此，在有机分子中构建这类C-S键在药物化学中有重要意义。苯炔作为一种高活性的亲电试剂，被广泛应用于C-S键的构建，常通过与烯丙基亚砜、二芳基亚砜，磺酰氟等发生插入、偶联反应一锅法形成C-S键，此类反应条件温和，操作简便。本文主要描述了苯炔和硫代磺酸酯参与C-S键构建反应研究，主要包括以下两部分内容：

第一部分主要介绍了无过渡金属催化的苯炔与硫代磺酸酯合成非对称芳基砜反应研究。通过改变硫代磺酸酯和苯炔前体上的取代基对反应进行了底物普适性研究，以中等至优异的产率成功构筑了25种化合物。通过控制实验、同位素标记实验及气相色谱-质谱联用仪对反应机理进行了研究，对该反应提出了一条可能的反应机理。本实验还对该反应进行了克级规模的反应研究，产率为93%。该实验开发了一种无过渡金属参与的，反应条件温和的快速构建C-S键的新方法。

第二部分介绍了苯炔参与的三组分反应合成N-磺酰基硫亚胺类化合物的反应研究。通过廉价易得的苯炔、硫代磺酸酯和磺酰胺三组分一锅法反应快速构建一系列硫亚胺化合物。该反应具有良好的底物普适性，共合成目标化合物52种，产率中等至良好，所有的产物结构均经过核磁共振氢谱、碳谱、高分辨质谱进行确认了。该反应能进行克级规模放大，产率为82%。该方法为在温和且无过渡金属催化条件下，高效合成硫亚胺提供了一种新途径。

Organic sulfur compounds exist widely in the fields of pharmaceutical chemistry, biochemistry, organic synthesis and material science. In particular, sulfone compounds in organic sulfides and sulfilimines have good applications in drugs. Therefore, the construction of this kind of C-S bond in organic molecules is of great significance in pharmaceutical chemistry. As a highly active electrophilic reagent, benzyne is widely used in the construction of C-S bond. It is often intercalated with allyl sulfoxide, diaryl sulfoxide and sulfonyl fluoride to form C-S bond by one-pot reaction. This kind of reaction conditions are mild and easy to operate. This thesis mainly describes the participation of benzyne and thiosulfonate in the construction of C-S bond, which mainly includes the following two parts:

The first part mainly introduces the synthesis of asymmetric aryl sulfone from benzyne and thiosulfonate without transition metal catalysis. The substrate universality of the reaction was studied by changing the substituents on the thiosulfonates and benzyne precursors, and 25 compounds were successfully constructed in medium to excellent yields. The reaction mechanism was studied by control experiment, isotope labeling experiment and gas chromatography-mass spectrometry (GC-MS), and a possible reaction mechanism was proposed. In this experiment, the reaction was also studied on the gram scale, and the yield was 93%. In this experiment, a new method for rapid construction of C-S bond without transition metal participation and mild reaction conditions was developed.

The second part introduces the study on the synthesis of N-sulfilimines by the three-component reaction of benzyne. A series of sulfilimines compounds were quickly constructed by the one-pot reaction of benzynes, thiosulfonates and sulfonamides. The reaction has good substrate universality. 52 target compounds were synthesized with medium to good yields. The structures of all the products were confirmed by ¹H NMR,¹³ C NMR and HRMS. The reaction can be enlarged on a gram scale and the yield is 82%. This method provides a new way for efficient synthesis of N-sulfilimines under mild and non-transition metal catalysis conditions.

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