Iron-Catalyzed C–H Sulfonylmethylation of Indoles in Water–PEG400

Shuai Lu; Yu-Shen Zhu; Ke-Xin Yan; Tian-Wei Cui; Xinju Zhu; Xin-Qi Hao; Mao-Ping Song

doi:10.1055/s-0039-1690675

Synlett, Inhaltsverzeichnis

Synlett 2019; 30(16): 1924-1928
DOI: 10.1055/s-0039-1690675

letter

Iron-Catalyzed C–H Sulfonylmethylation of Indoles in Water–PEG400

Shuai Lu

,

Yu-Shen Zhu

,

Ke-Xin Yan

,

Tian-Wei Cui

,

Xinju Zhu ∗

,

Xin-Qi Hao∗

,

Mao-Ping Song

Abstract

Alle Artikel dieser Rubrik

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.

Key words

indoles - sulfonylmethylation - p-toluenesulfonylmethyl isocyanide

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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.

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