Citation: Liu Wen-Qiang, Yang Xiu-Long, Tung Chen-Ho, Wu Li-Zhu. Activation of S-H and N-H Bonds to Synthesize Sulfinamides via Cross Coupling Hydrogen Evolution[J]. Acta Chimica Sinica, ;2019, 77(9): 861-865. doi: 10.6023/A19030077 shu

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

Liu Wen-Qiang ^a,b ,
Yang Xiu-Long ^a,b ,
Tung Chen-Ho ^a,b ,
Wu Li-Zhu ^a,b,,

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

Corresponding author: Wu Li-Zhu, lzwu@mail.ipc.ac.cn
Received Date: 6 March 2019
Available Online: 22 September 2019
Fund Project: the Strategic Priority Research Program of the Chinese Academy of Science XDB17000000the National Natural Science Foundation of China 91427303Key Research Program of Frontier Sciences of the Chinese Academy of Science QUZDY-SSW-JSC029the National Natural Science Foundation of China 21861132004the Ministry of Science and Technology of China 2017YFA0206903Project supported by the Ministry of Science and Technology of China (2017YFA0206903), the National Natural Science Foundation of China (91427303 and 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), and K. C. Wong Education Foundation

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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. H₂¹⁸O 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.
- electrochemical catalysis,
- radical pathway,
- cross coupling hydrogen evolution,
- sulfinamides
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