Iodine-Promoted Synthesis of 4-Aryl-2-(arylsulfonyl)quinolones by Desulfurative C–S Cross-Coupling Reaction of Quinoline-2-thiones with Sodium Sulfinates

Abstract

An iodine-induced sulfonylation of quinoline-2-thiones with sodium arenesulfinates as sulfur sources for the synthesis of 4-aryl-2-(arylsulfonyl)quinoline derivatives is described. The 4-aryl-2-(arylsulfonyl)quinoline derivatives can be obtained in a moderate to good yields. This C–S bond cleavage and C–S cross-coupling proceeds in the absence of a metal under inexpensive and nontoxic conditions and it displays a broad substrate scope.

Key words

C–S cross-coupling - quinolinethiones - arylsulfonylquinolines - C–S bond cleavage - sodium sulfonate - iodine catalysis

• References and Notes

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• 19 6-Methyl-4-phenyl-2-tosylquinoline (3a); Typical Procedure The mixture of 6-methyl-4-phenylquinoline-2(1H)-thione (1a; 0.2 mmol, 50 mg), sodium 4-methylbenzenesulfinate (2a; 0.5 mmol, 89 mg), and I₂ (0.25 mmol, 26 mg) in DMSO (2 mL) was stirred at 100 °C for 4 h under air. When the reaction was complete (TLC), sat. aq Na₂SO₃ was added to quench the reaction, and the resulting mixture was extracted with EtOAc (3 × 25 mL). The combined organic layers were dried (MgSO₄), filtered, and concentrated in vacuum. The residue was purified by column chromatography [silica gel, EtOAc–PE (1:12)] to give a white solid; yield: 64 mg (87%); mp 154–157 ℃. ¹H NMR (400 MHz, CDCl₃): δ = 8.14 (d, J = 8.8 Hz, 1 H), 8.11 (s, 1 H), 8.05 (d, J = 8.4 Hz, 2 H), 7.70 (s, 1 H), 7.61 (dd, J = 8.8, 8.8 Hz, 1 H), 7.57–7.53 (m, 3 H), 7.50 (m, 7.51–7.50, 2 H), 7.34 (d, J = 8.4 Hz, 2 H), 2.48 (s, 3 H), 2.40 (s, 3 H). ¹³C NMR (150 MHz, CDCl₃): δ = 157.0, 150.5, 146.7, 144.7, 139.6, 137.2, 136.4, 133.0, 130.5, 129.8, 129.5, 129.0, 129.0, 128.8, 124.5, 117.8, 22.02, 21.6. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₃H₂₀NO₂S: 374.1209; found: 374.1206.