化学学报 ›› 2019, Vol. 77 ›› Issue (9): 861-865.DOI: 10.6023/A19030077 上一篇    下一篇

所属专题: 有机自由基化学

研究通讯

S—H键和N—H键交叉偶联放氢制备亚磺酰胺

刘文强ab, 杨修龙ab, 佟振合ab, 吴骊珠*()   

  1. a中国科学院理化技术研究所 光化学转换与功能材料重点实验室 北京 100190
    b中国科学院大学 未来技术学院 北京 100049
  • 收稿日期:2019-03-06 出版日期:2019-09-15 发布日期:2019-04-22
  • 通讯作者: 吴骊珠 E-mail:lzwu@mail.ipc.ac.cn
  • 基金资助:
    项目受中国科学技术部(2017YFA0206903);国家自然科学基金(91427303);国家自然科学基金(21861132004);中国科学院战略优先研究计划(XDB17000000);中国科学院前沿科学重点研究项目(QUZDY-SSW-JSC029);王宽诚教育基金会资助

Activation of S—H and N—H Bonds to Synthesize Sulfinamides via Cross Coupling Hydrogen Evolution

Liu, Wen-Qiangab, Yang, Xiu-Longab, Tung, Chen-Hoab, Wu, Li-Zhu*()   

  1. a Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190
    b School of Future Technology, University of Chinese Academy of Sciences, Beijing 100049
  • Received:2019-03-06 Online:2019-09-15 Published:2019-04-22
  • Contact: Wu, Li-Zhu E-mail:lzwu@mail.ipc.ac.cn
  • Supported by:
    Project supported by the Ministry of Science and Technology of China(2017YFA0206903);the National Natural Science Foundation of China(91427303);the National Natural Science Foundation of China(21861132004);the Strategic Priority Research Program of the Chinese Academy of Science(XDB17000000);Key Research Program of Frontier Sciences of the Chinese Academy of Science(QUZDY-SSW-JSC029);K. C. Wong Education Foundation

利用交叉偶联放氢的方法, 实现了电化学一体池中苯硫酚类化合物与胺类化合物间N—S键的构筑, 高效地制备了一系列亚磺酰胺化合物. 实验结果证实, 该反应通过自由基路径生成的次磺酰胺, 以反应溶剂中微量的水为氧源, 进一步电催化氧化得到亚磺酰胺. 四正丁基碘化铵在反应中可起到电解质和中间体的双重作用.

关键词: 电化学催化, 自由基路径, 交叉偶联放氢, 亚磺酰胺

Catalytic synthesis of organic sulfinamides has great significance and value in organic synthesis, material science, and bioscience. Traditional synthetic methods for sulfinamides are often confronted with various challenges, such as tedious reaction steps, harsh reaction conditions. Direct activation of S—H and N—H bonds to synthesis sulfinamides is the most effective and atomic economic way, which can realize the N—S bonds construction without pre-functionalization of the substrates. To establish a versatile and efficient technology for such reaction, an electrochemical cross coupling hydrogen evolution (CCHE) reaction, which is often used as an environmentally friendly and efficient way to construct new bonds, for synthesis of sulfinamides has been successfully developed by using thiols and amines as the easily available and inexpensive substrates. A series of sulfinamides were prepared with excellent yields and good compatibility of functional groups under extremely mild reaction conditions. Experimental results showed that sulfenamides, which were constructed as intermediate products via radical pathway, were further oxidized to sulfinamides. H2 18O labeling experiment confirmed that the oxygen of sulfinyl group comes from the trace water in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP). In addition, tetrabutylammonium iodide (TBAI) played important dual roles of intermediate and electrolyte in this reaction system. The typical procedure is as follows: A 20 mL oven-dried reaction vital equipped with a magnetic stir bar was charged with thiol 1 (0.2 mmol), amine 2 (0.3 mmol) and TBAI (0.05 mol/L) in HFIP (5 mL), and exhausted via puncture needle for 15 minutes with argon. The mixture was then electrolysed with carbon foam plate (anode) and platinum plate (cathode) as the electrodes in an undivided cell for 6 hours in 10 mA constant current at room temperature. After the reaction, the mixture was evaporated under reduced pressure to remove the solvent and the residue was purified by chromatography on silica gel to get the desired sulfinamide 3.

Key words: electrochemical catalysis, radical pathway, cross coupling hydrogen evolution, sulfinamides