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Synthesis of 1,3-Dibenzenesulfonylpolysulfane (DBSPS) and Its Application in the Preparation of Aryl Thiosulfonates from Boronic Acids

Yi-Fan Jiang, Wei-Chen Zhu, Xin-Yu Liu, Shi-Yin Tian, Jia-Hui Han, Weidong Rao, Shu-Su Shen, Daopeng Sheng and Shun-Yi Wang*

*Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering, Soochow University, Suzhou 215123, China, Email: shunyisuda.edu.cn

Y.-F. Jian, W.-C. Zhu, X.-Y. Liu, S.-Y. Tian, J.-H. Han, W. Rao, S.-S. Shen, D. Sheng, S.-Y. Wang, Org. Lett., 2023, 25, 1776-1761.

DOI: 10.1021/acs.orglett.3c00526


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Abstract

A method for the synthesis of 1,3-dibenzenesulfonylpolysulfane (DBSPS) is described. DBSPS further reacts with boronic acids to afford thiosulfonates.

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General procedures for synthesis of products

PhSO2Na (10g, 61 mmol) and sulfur (1.95 g, 61 mmol) were weighed into a 250 ml round-bottom flask with a mechanical stirrer. Pyridine (60 mL) was then added, and the mixture was stirred at room temperature for 10 h. The mixture was filtered, and the residue was washed with ether three times. PhSO2SNa (1083 g, 92% yield) was obtained as a white solid and used without further purification

Sodium Thiosulfonate (10 mmol, 1.0 equiv.) were added to a dry Schlenk tube. The flask was evacuated and backfilled with N2 for 3 times. Then CHCl3 (10 mL) was added with syringe. After 10 min CH3COCl (15 mmol, 1 mL) was added. The mixture was stirred at room temperature for 10 h. After the reaction was complete, the mixture was diluted with ethyl acetate and washed with water (20 mL 3). Then the organic phase was combined and dried over anhydrous MgSO4. The solvent was removed under vacuum and the residue was purified by flash column chromatography on silica gel to provide the product. In particular, the mixtures are similar in polarity and cannot be separated. However, from the high resolution mass spectrometry, the main products we get are dibenzenesulfonylpolysulfane compounds (n = 3).

In glovebox, an oven-dried screw-capped 8 mL vial equipped with a magneticstir bar was charged with 1 (0.08 g), 2 (0.2mmol) and Cu(OSO2CF3)2 (72 mg, 0.2 mmol), CH3OH (2.0 mL) was added via syringe. The reaction mixture was stirred at 60 C in oil bath for 12 h. After 12h, the crude reaction mixture was diluted with ethyl acetate (20 mL) and washed with water (20 mL 3). The organic layer was dried over MgSO4. The residue was purified by flash chromatography EtOAc and PE (EA :PE=1:20).


Key Words

thiosulfonates


ID: J54-Y2023