摘要：有机磷化合物在有机合成、功能材料以及药物化学等领域具有广泛应用。其中，含硫有机磷化合物，如硫代磷酸酯，因其显著的生物活性而被越来越多的引起关注。传统合成硫代膦酸酯的方法大多采用毒性较强的磷酰氯以及较为苛刻的反应条件。如何简单、高效合成此类化合物已成为有机磷化学研究方向的热点。

本论文工作主要集中在二价金属铜盐催化下P-S-C键化合物的构建方法探索。通过对sp2杂化碳原子成键模型反应（C-X）的设计以及反应条件的优化，将磺酰氯和磷试剂进行交叉偶联制备硫代磷酸酯类化合物。通过氨基酸配体的调控，更大程度的提高了此类反应的效率，并在此基础上进一步拓展反应底物适用范围。藉此，深入系统地开展此类配体辅助过渡金属催化的交叉偶联反应将对基础有机化学、药物化学、材料化学以及催化学科产生较重要的意义。70211

毕业论文关键词：硫代膦酸酯；P-S-C键；交叉偶联；铜催化

Cu-catalyzed P-S-C bond formation

Abstract：Organophosphorus compounds are widely used in organic synthesis, functional materials, pharmaceutical chemistry and other fields.  Such as thiophosphonates, have attracted more and more attention because of their remarkable biological activities. Most of the traditional methods for synthesizing phosphorothioate are phosphorus chloride with strong toxicity and relatively harsh reaction conditions. How to synthesis of these compounds simple and efficient  has become the focus of organic phosphorus chemical research.

 The main work of this thesis is focused on the construction methods of P-S-C bond compounds under the catalysis of two valence metal copper salts. Through the design of SP2 hybrid carbon bond model reaction (C-X) and the optimization of reaction conditions, cross coupling of sulfonyl chloride and phosphorus reagent was used to prepare phosphorothioate compounds. Through the regulation of amino acid ligand, the efficiency of this kind of reaction is improved to a greater extent, and the applicable range of reaction substrate is further extended. Therefore, it is very important for the basic organic chemistry, medicinal chemistry, material chemistry and catalysis science to carry out the cross coupling reaction of the ligand assisted transition metal catalysis systematically and systematically.

 Keywords: thiophosphonates; P-S-C bond; cross-coupling; Cu-catalized

目 录

1绪论 1

1.1含硫化合物的简介 1

1.2 含硫化合物的应用 1

1.2.1含硫香料 1

1.2.2含硫农药 2

1.2.3含硫材料 3

1.2.4含硫生物学 3

1.2.5含硫药物 3

2构建P-S-C（SP2）键化合物方法研究 5

2.1 P-S-C键化合物的传统构建方法 5

2.2 Cu催化构建P-S-C(sp2杂化)键 5

3 铜催化P-S-C键化合物的实验部分 8

3.1 实验仪器和试剂 11

3.1.1 实验仪器 11

3.1.2 试剂材料 11

3.2实验部分 12

3.2.1反应的初步探索 13

3.2.2催化体系的筛选 13