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Synlett 2020; 31(04): 349-354
DOI: 10.1055/s-0039-1691563
DOI: 10.1055/s-0039-1691563
letter
TMSOTf-Promoted Sulfinylation of Electron-Rich Aromatics with Sodium Arylsulfinates
This project was funded by the Key Research and Development Program of Shandong (Grant No. 2019GSF108089), the Natural Science Foundation of Shandong Province (ZR2019MB009), the National Natural Science Foundation of China (Grant No. 21672046 and 21372054), and the Found from the Huancui District of Weihai City.Further Information
Publication History
Received: 03 October 2019
Accepted after revision: 16 December 2019
Publication Date:
09 January 2020 (online)
Abstract
A new transition-metal-free route for the direct sulfinylation of electron-rich aromatics with sodium arylsulfinates in the presence of TMSOTf is reported. Various electron-rich aromatics, including pyrroles, thiophenes, indoles, and electron-rich arenes, with sodium arylsulfinates are converted into the corresponding sulfoxides in moderate to excellent yields. This protocol possesses many advantages such as readily available and stable starting materials, broad substrate scopes, and transition-metal-free reaction conditions.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0039-1691563.
- Supporting Information
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- 17 General Procedure for the Preparation of Sulfoxides 4 The mixture of sodium arylsulfinate (0.2 mmol, 1.0 equiv), pyrrole/thiophenes (0.3 mmol, 1.5 equiv), and TMSOTf (0.4 mmol, 2.0 equiv) in (ClCH2)2 (1.0 mL) was stirred at 25 °C for 0.5 h. After completion of the reaction, water (5 mL) and dichloromethane (10 mL) were added. The two layers were separated, and the aqueous phase was extracted with dichloromethane (3 × 10 mL). The combined organic extracts were washed by brine, dried over anhydrous Na2SO4, filtered, and concentrated. The residue was purified by flash chromatography on silica gel (ethyl acetate–petroleum ether = 1:1) to afford the desired sulfoxides 4. Compound 4a: white solid, mp 84–86 °C; 36.3 mg, 83% yield. 1H NMR (400 MHz, CDCl3): δ = 7.53 (d, J = 8.2 Hz, 2 H), 7.27 (d, J = 8.0 Hz, 2 H), 6.95 (t, J = 2.0 Hz, 1 H), 6.58 (t, J = 2.5 Hz, 1 H), 6.16 (dd, J = 3.0, 1.7 Hz, 1 H), 3.64 (s, 3 H), 2.39 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 141.9, 140.3, 129.3, 126.8, 124.5, 124.3, 123.9, 107.4, 36.4, 21.2. Data are in accordance to those previously reported.13a General Procedure for the Preparation of Sulfoxides 10 The mixture of sodium arylsulfinate (0.2 mmol, 1.0 equiv), indole (0.4 mmol, 2.0 equiv), and TMSOTf (0.4 mmol, 2.0 equiv) in (ClCH2)2 (1.0 mL) was stirred at 25 °C for 0.5 h. After completion of the reaction, water (5 mL) and dichloromethane (10 mL) were added. The two layers were separated, and the aqueous phase was extracted with dichloromethane (3 × 10 mL). The combined organic extracts were washed by brine, dried over anhydrous Na2SO4, filtered, and concentrated. The residue was purified by flash chromatography on silica gel (ethyl acetate–petroleum ether = 1:1) to afford the desired sulfoxides 10. Compound 10a: white solid, mp 138–139 °C; 42.0 mg, 78% yield. 1H NMR (400 MHz, CDCl3): δ = 7.62 (d, J = 8.2 Hz, 2 H), 7.48 (d, J = 8.7 Hz, 2 H),7.34–7.24 (m, 4 H), 7.12–7.08 (m, 1 H), 3.79 (s, 3 H), 2.40 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 140.9, 140.3, 137.6, 132.5, 129.5, 124.8, 124.3, 123.2, 121.3, 119.8, 116.5, 110.0, 33.2, 21.2. Data are in accordance to those previously reported.13a General Procedure for the Preparation of Sulfoxides 12 The mixture of sodium arylsulfinate (0.2 mmol, 1.0 equiv), arene (0.4 mmol, 2.0 equiv), and TMSOTf (0.4 mmol, 2.0 equiv) in (ClCH2)2 (1.0 mL) was stirred at 25 °C for 1 h. After completion of the reaction, water (5 mL) and dichloromethane (10 mL) were added. The two layers were separated, and the aqueous phase was extracted with dichloromethane (3 × 10 mL). The combined organic extracts were washed by brine, dried over anhydrous Na2SO4, filtered, and concentrated. The residue was purified by flash chromatography on silica gel (ethyl acetate–petroleum ether = 1:1) to afford the desired sulfoxides 12. Compound 12a: colorless oil, 27.0 mg, 55% yield. 1H NMR (400 MHz, CDCl3): δ = 7.55 (d, J = 8.8 Hz, 2 H), 7.49 (d, J = 8.1 Hz, 2 H), 7.25 (d, J = 7.3 Hz, 2 H), 6.95 (d, J = 8.8 Hz, 2 H), 3.81 (s, 3 H), 2.36 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 161.8, 142.5, 141.2, 136.9, 129.8, 127.0, 124.7, 114.7, 55.4, 21.3. Data are in accordance to those previously reported.11a