Iron(III)-Catalyzed Radical Cross-Coupling of Thiols with Sodium Sulfinates: A Facile Access to Thiosulfonates

Abstract

A convenient and efficient synthesis of symmetrical and asymmetric thiosulfonates from thiols and sodium sulfinates is reported. The protocol involves iron(III)-catalyzed formation of sulfenyl and sulfonyl radicals in situ under aerobic conditions and their subsequent cross-coupling to afford thiosulfonates in 83–96% yield. The utilization of readily available, nontoxic, and inexpensive iron(III) as a catalyst and atmospheric oxygen as an oxidant is within the confines of green and sustainable chemistry.

Key words

sulfonates - thiols - thiosulfonates - iron - catalysis - oxidation

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• 28 Thiosulfonates 3; General Procedure A mixture of the appropriate thiol 1 (0.5 mmol), sodium thiosulfinate 2 (1.0 mmol), and FeCl₃ (20 mol%) in DMF (3 mL) was stirred at r.t. for 30–60 min under air in a round-bottomed flask. When the reaction was complete (TLC), H₂O (5 mL) was added and the mixture was extracted with EtOAc (3 × 5 mL). The combined organic phases were dried (Na₂SO₄), filtered, and concentrated under reduced pressure. The residue was purified by column chromatography using a gradient mixture of hexane and EtOAc as eluent. S-Phenyl 4-Toluenethiosulfonate (Table 3, Entry 1) Colorless solid; yield: 126 mg (96%); mp 74–75 °C. IR (KBr): 1130, 1315 (SO₂) cm^–1. ¹H NMR (400 MHz, CDCl₃, TMS): δ = 2.40 (s, 3 H) 7.31 (t, 2 H, J = 6.8 Hz), 7.34 (t, 2 H, J = 6.8 Hz), 7.40–7.44 (m, 2 H), 7.58 (d, 2 H, J = 8.4 Hz), 7.48 (d, 1 H, J = 8.8 Hz). ¹³C NMR (100 MHz, CDCl₃, TMS): δ = 28.3, 127.4, 127.9, 128.8, 129.3, 131.5, 133.5, 136.6, 143.0. EIMS: m/z = 264 [M⁺]. Anal. Calcd for C₁₃H₁₂O₂S₂: C, 59.06; H, 4.58. Found: C, 59.28; H, 4.45. S-(4-Fluorophenyl) 4-Fluorobenzenethiosulfonate (Table 3, Entry 3) Colorless crystal; yield: 132 mg (92%); mp 68–70 °C. IR (KBr): 1229, 1330 (SO₂) cm^–1. ¹H NMR (400 MHz, CDCl₃, TMS): δ = 7.10 (d, 2 H, J = 8.4 Hz), 7.16 (t, 2 H, J = 8.4 Hz), 7.35 (dd, 2 H, J = 5.2 Hz, J = 9.0 Hz), 7.63 (dd, 2 H, J = 4.8 Hz, J = 9.6 Hz). ¹³C NMR (100 MHz, CDCl₃, TMS): δ = 116.4, 117.0, 123.2, 123.7, 130.1, 138.7, 163.9, 166.1. EIMS: m/z = 286 [M⁺]. Anal. Calcd for C₁₂H₈F₂O₂S₂: C, 50.34; H, 2.82. Found: C, 50.54; H, 2.76. S-(3-Nitrophenyl) 4-Toluenethiosulfonate (Table 3, Entry 5) Colorless crystal; yield: 139 mg (90%); mp 97–99 °C. IR (KBr): 1140, 1331 (SO₂) cm^–1. ¹H NMR (400 MHz, CDCl₃, TMS): δ = 2.39 (s, 3 H), 7.24–7.28 (m, 2 H), 7.40–7.49 (m, 2 H), 7.64 (t, J = 8.0 Hz, 1 H), 7.83–7.86 (m, 1 H), 8.02 (s, 1 H), 8.32–8.39 (m, 1 H). ¹³C NMR (100 MHz, CDCl₃, TMS): δ = 21.2, 125.6, 127.4, 129.8, 130.4, 130.5, 131.0, 139.5, 142.0, 145.7, 148.3. EIMS: m/z = 309 [M⁺]. Anal. Calcd for C₁₃H₁₁NO₄S₂: C, 50.47; H, 3.38; N, 4.53. Found: C, 50.26; H, 3.49; N, 4.80. S-(4-Chlorophenyl) 4-Chlorobenzenethiosulfonate (Table 3, Entry 7) Colorless crystal; yield: 149 mg (94%); mp 134–136 °C. IR (KBr): 1140, 1330 (SO₂) cm^–1. ¹H NMR (400 MHz, CDCl₃, TMS): δ = 7.35 (d, 2 H, J = 8.4 Hz), 7.39 (d, 2 H, J = 8.8 Hz), 7.46 (d, 2 H, J = 9.2 Hz), 7.52 (d, 2 H, J = 8.8 Hz). ¹³C NMR (100 MHz, CDCl₃, TMS): δ = 128.8, 129.3, 130.0, 130.4, 137.7, 138.5, 140.5, 141.2. EIMS: m/z = 318 [M⁺], 320 [M + 2]⁺, 322 [M + 4]⁺. Anal. Calcd for C₁₂H₈Cl₂O₂S₂: C, 45.15; H, 2.53. Found: C, 45.00; H, 2.75.