惰性芳香烃C-H活化偶联C-S成键

C-S coupling to thio- compounds is an important process in chemical industry that is widely used in preparing kinds of products such as medicines, pesticides, and function materials. Traditional methods for C-S coupling is usually achieved under cleavage of an active C-X (X = Cl, Br, I, N, C, O, etc.) bond; these approaches are not only substrate-selective but also of poor atom economy, limiting their application in industry. Green approach for C-S bond formation is highly demanding. Our project is aiming at preparing thio- compounds by breaking the C-H bond of unactivated arene coupled with making the C-S bond; lanthanide complexes will be used as catalyst. The investigation will start from gas-phase ion-molecule reaction to prob the ideal model for activating the C-H bond of arenes and meanwhile, achieving C-S coupling. Further, rational design of condensed-phase sulfurication of unactivated arenes will be performed and guided by gas-phase models as established in advance. Our work will contribute to the greenization of fine-chemistry industry and to the development of chemical science.

C-S偶联制备含硫化合物是化学工业中一类重要的反应过程，是生产多种医药、农药及新型功能材料的重要步骤。传统C-S偶联通常在断裂活泼C-X（X = Cl, Br, I, N, C, O等）键的基础上进行，除了应用范围有限外，反应过程原子经济性亦较差，制约了其在工业中的应用。开发C-S成键绿色方案亟待进行。本项目提出一种以惰性芳香烃和硫磺为原料，以镧系金属配合物为催化剂，催化惰性芳香烃C-H活化偶联C-S成键的反应方案。研究工作将从气相离子-分子反应出发，在分子水平下探索活化芳香烃C-H键并实现C-S偶联的理想催化剂模型；在此基础之上，理性设计液相实验方案，并以气相反应得到的信息为指导进行探索和改进。相关研究工作的进行对推动精细化学工业绿色化及相关学科的发展均具有重要意义。

C-S偶联制备含硫化合物是化学工业中一类重要的反应过程，是生产多种医药、农药及新型功能材料的重要步骤。传统C-S偶联的一个重要途径是磺化-还原过程，不仅过程危险性较大，三废排放也较严重；虽然近年来已有用有机硫试剂进行温和条件下C-S偶联的报道，但其所用试剂较为昂贵，难以大规模应用。本项目气相离子-分子反应出发，在分子水平下探索了硫原子及硫团簇与不同烃类化合物之间作用原理，对C-H、C-S、S-H成键及活化规律进行了总结。在此基础上，设计了脂肪烃/芳香烃C-H键活化并C-S偶联的反应体系，开发了一系列液相构筑C-S键的方案。相关研究工作成果有望在精细化学品生产领域得到应用，推动含硫精细化学品清洁生产。