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Synlett 2019; 30(16): 1924-1928
DOI: 10.1055/s-0039-1690675
DOI: 10.1055/s-0039-1690675
letter
Iron-Catalyzed C–H Sulfonylmethylation of Indoles in Water–PEG400
Autor*innen
Financial support from the National Natural Science Foundation of China (Grant No. 21672192 and 21803059), the China Postdoctoral Science Foundation (Grant No. 2016M602254 and 2016M600582), the Program for Science & Technology Innovation Talents in Universities of Henan Province (Grant No. 17HASTIT004), the Aid Project for the Leading Young Teachers in Henan Provincial Institutions (Grant No. 2015GGJS-157), and the Natural Science Foundation of Henan Province (Grant No. 182300410255) is gratefully appreciated.
Weitere Informationen
Publikationsverlauf
Received: 18. Juni 2019
Accepted after revision: 23. August 2019
Publikationsdatum:
10. September 2019 (online)
Abstract
An iron-catalyzed C–H sulfonylmethylation of indoles in water–PEG400 has been developed using p-toluenesulfonylmethyl isocyanide. This protocol enables direct regioselective construction of Csp2–Csp3 bond at the C3 position of indoles with a broad range of substrate compatibility in moderate to good yields, which is cost-effective and environmentally friendly.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0039-1690675.
- Supporting Information (PDF) (opens in new window)
-
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- 22 General Procedure for Preparation of Products 3 and 4To a 15 mL two-necked Schlenk tube fitted with glass stopper were added indoles 1 (0.1 mmol), TosMIC derivatives 2 (0.3 mmol), and FeSO4·7H2O (0.015 mmol, 4.2 mg) in a mixed solvent of H2O and PEG400 (v/v = 3:2, 2 mL) under an Ar atmosphere using the standard Schlenk techniques. The Schlenk tube was capped and heated at 110 °C for 24 h. The reaction mixture was then cooled to room temperature and concentrated directly. After removal of solvent, the residue was purified by preparative thin-layer chromatography (petroleum ether/EtOAc = 1:1) to give the desired product 3 and 4.4-Fluoro-3-(tosylmethyl)-1H-indole (3b)Brown solid (28.3 mg, 93%), mp 162–163 °C. 1H NMR (600 MHz, CDCl3): δ = 8.70 (s, 1 H), 7.59 (d, J = 7.4 Hz, 2 H), 7.18–7.16 (m, 3 H), 7.07–7.06 (m, 1 H), 7.01–6.98 (m, 1 H), 6.60 (t, J = 9.2 Hz, 1 H), 4.64 (s, 2 H), 2.36 (s, 3 H). 13C{1H} NMR (150 MHz, CDCl3): δ = 156.7 (d, J = 244.9 Hz), 144.5, 138.3 (d, J = 10.8 Hz), 135.5, 129.2, 128.5, 126.2, 122.8 (d, J = 8.0 Hz), 116.0 (d, J = 18.8 Hz), 107.6 (d, J = 3.6 Hz), 105.2 (d, J = 19.2 Hz), 100.6, 54.8, 21.6. 19F NMR (565 MHz, CDCl3): δ = –124.6. HRMS (positive ESI): m/z [M + Na]+ calcd for C16H14FNNaO2S+: 326.0621; found: 326.0621.