Copper-Mediated Direct Sulfenylation of 4-Hydroxyquinolinones and 4-Hydroxypyridones with Aryl Thiols via a C−H Functionalization Process

Abstract

An efficient approach for the direct sulfanylation of 4-hydroxyquinolinones and 4-hydroxypyridones with aryl thiols in the presence of CuI/DMSO has been developed. The substrate scope is broad, allowing facile synthesis of a range of structurally diverse 3-sulfanyl-4-hydroxyquinolinones and 3-sulfanyl-4-hydroxypyridones in good efficiency.

Key words

sulfanylation - C–H functionalization - quinolinones - pyridones - C–S bond

• References and Notes

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• 17 General Procedure: DMF (0.5 mL) was added into a flask charged with 4-hydroxyquinolinone (0.25 mmol), aryl thiol (0.375 mmol), DMSO (58.6 mg), and CuI (23.7 mg, 0.125 mmol). The mixture was heated at 100 °C and stirred in a closed tube for 6 h, then cooled to room temperature, diluted with EtOAc (20 mL) and washed with H₂O (10 mL). The aqueous layer was extracted with EtOAc (2 × 5 mL) and the combined organic phase was dried over Na₂SO₄. After evaporation of the solvents the residue was purified by flash column chromatography (silica gel; PE/EtOAc, 3:1) to afford the desired products 3 and 5. 4-Hydroxy-1-methyl-3-(phenylthio)quinolin-2(1H)-one (3a): Yellow solid; mp 237–239 °C. ¹H NMR (400 MHz, CDCl₃): δ = 3.73 (s, 3 H), 7.14–7.18 (m, 1 H), 7.21–7.31 (m, 5 H), 7.39 (d, J = 8.4 Hz, 1 H), 7.65 (td, J = 1.6, 8.4 Hz, 1 H), 7.85 (s, 1 H), 8.07 (dd, J = 1.6, 8.0 Hz, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 30.3, 102.4, 114.3, 114.4, 122.2, 125.1, 126.8, 128.0, 129.3, 132.9, 134.3, 140.5, 161.7, 163.5. IR (KBr): 2927, 2844, 2368, 1618, 1581, 1471, 1275, 1161, 762, 742 cm^–1. HRMS: m/z [M⁺+H] calcd for C₁₆H₁₄NO₂S⁺: 284.07398; found: 284.07385. 4-Hydroxy-1,6-dimethyl-3-(phenylthio)pyridin-2(1H)-one (5a): Yellow solid; mp 154–156 °C. ¹H NMR (400 MHz, CDCl₃): δ = 2.37 (s, 3 H), 3.51 (s, 3 H), 6.02 (s, 1 H), 7.11–7.17 (m, 1 H), 7.20–7.23 (m, 4 H), 7.37 (s, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 21.5, 31.8, 98.6, 99.3, 126.4, 127.5, 129.2, 135.0, 149.6, 163.6, 166.9. IR (KBr): 2922, 2852, 2360, 1653, 1568, 1471, 1404, 1373, 1149, 1024, 831, 748 cm^–1. HRMS: m/z [M⁺+H] calcd for ­C₁₃H₁₄NO₂S⁺: 248.07398; found: 248.07405.