Tetrabutylammonium Iodide Mediated Synthesis of β-Alkoxy Sulfides and Vinyl Sulfones by Using Benzenesulfonyl Chlorides as the Sulfur Sources under Acidic or Alkaline Conditions

Abstract

The tetrabutylammonium iodide (TBAI)-promoted generation of sulfur-containing compounds from benzenesulfonyl chlorides and alkenes is described. Under acidic condition, a wide range of β-alkoxy sulfides were obtained in good to excellent yields, whereas under alkaline conditions, various vinyl sulfones were produced in moderate to good yields. A novel preparation of (E)-β-iodovinyl sulfones was achieved through direct difunctionalization of alkynes with benzenesulfonyl chlorides and TBAI.

Key words

arenesulfonyl chlorides - oxysulfenylation - aralkenes - aralkynes - sulfides - sulfones

• References and Notes

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• 15 β-Alkoxy Sulfides 4; General Procedure40% aq HBr (117 μL, 0.8 mmol) was added to a solution of the appropriate benzenesulfonyl chloride 1 (0.20 mmol), styrene 2 (0.24 mmol), alcohol 3 (0.8 mmol), and TBAI (295.5 mg, 0.8 mmol) in EtOAc or DCE (2 mL), and the mixture was stirred at 80 °C for 15 h in a sealed Schlenk tube. When the reaction was complete, the mixture was diluted with EtOAc, the reaction was quenched with sat. aq Na₂S₂O₃ (10 mL), and the mixture was extracted with EtOAc (2 × 15 mL). The organic layer was washed with H₂O, dried (Na₂SO₄), and concentrated in vacuo. The residue was purified by column chromatography (silica gel, EtOAc–PE).1-[(2-Ethoxy-2-phenylethyl)sulfanyl]-4-methylbenzene (4a)Colorless oil; yield: 46.3 mg (85%). ¹H NMR (400 MHz, CDCl₃): δ = 7.35–7.25 (m, 7 H), 7.08 (d, J = 8.0 Hz, 2 H), 4.39–4.35 (m, 1 H), 3.42–3.26 (m, 3 H), 3.09–3.05 (m, 1 H), 2.31 (m, 3 H), 1.17 (t, J = 8.0 Hz, 3 H).1-{1-Ethoxy-2-[(4-tolyl)sulfanyl]ethyl}-4-nitrobenzene (4h)Colorless oil; yield: 45.6 mg (72%). 1H NMR (400 MHz, CDCl₃): δ = 8.18 (d, J = 8.0 Hz, 2 H), 7.47 (d, J = 8.0 Hz, 2 H), 7.24 (d, J = 8.0 Hz, 2 H), 7.09 (d, J = 8.0 Hz, 2 H), 4.47–4.44 (m, 1 H), 3.41–3.31 (m, 3 H), 3.27–3.03 (m, 1 H), 2.32 (s, 3 H), 1.19 (t, J = 8.0 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 148.8, 147.6, 136.7, 131.9, 130.5, 129.8, 127.6, 123.7, 80.0, 65.3, 41.9, 21.0, 15.2. HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₇H₁₉NNaO₃S: 340.0978; found: 340.0972.1-{[2-(Benzyloxy)-2-phenylethyl]sulfanyl}-4-methylbenzene (4k)Colorless oil; yield: 41.4 mg (62%). ¹H NMR (600 MHz, CDCl₃): δ = 7.36–7.21 (m, 12 H), 7.05 (d, J = 4.0 Hz, 2 H), 4.49–4.47 (m, 2 H), 4.29 (d, J = 4.0 Hz, 1 H), 3.37–3.34 (m, 1 H), 3.12–3.09 (m, 1 H), 2.30 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 140.7, 138.0, 136.1, 132.8, 130.1, 129.7, 128.6, 128.3, 128.2, 127.8, 127.7, 127.6, 80.1, 70.8, 42.4, 21.0. HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₂H₂₂NaOS: 357.1284; found: 357.1280.
• 16 Vinyl Sulfones 5; General ProcedureEt₃N (56 μL, 0.4 mmol) was added to a solution of the appropriate benzenesulfonyl chloride 1 (0.40 mmol), styrene 2 (0.20 mmol), and TBAI (147.8 mg, 0.4 mmol) in DME (1 mL), and the mixture was stirred at 100 °C for 15 h in a sealed Schlenk tube. When the reaction was complete, the mixture was diluted with EtOAc, the reaction was quenched with sat. aq Na₂S₂O₃ (10 mL), and the mixture was extracted with EtOAc (2 × 15 mL). The organic layer was washed with H₂O, dried (Na₂SO₄), and concentrated in vacuo. The residue was purified by column chromatography (silica gel, EtOAc–PE).1-Methyl-4-{[(E)-2-phenylvinyl]sulfonyl}benzene (5a)White solid; yield: 38.7 mg (75%); mp 120–122 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.83 (d, J = 4.0 Hz, 2 H), 7.66 (d, J = 8.0 Hz, 1 H), 7.46 (s, 2 H), 7.35 (t, J = 8.0 Hz, 5 H), 6.86 (d, J = 8.0 Hz, 1 H), 2.42 (s, 3 H).
• 17 (E)-β-Iodovinyl Sulfones 7; General ProcedureTBAI (147.8 mg, 0.4 mmol) was added to a solution of the appropriate benzenesulfonyl chloride 1 (0.40 mmol) and aralkyne 2 (0.20 mmol) in DME (1 mL), and the mixture was stirred in a sealed tube at reflux for 5 h. When the reaction was complete, the mixture was diluted with EtOAc, the reaction was quenched with sat. aq Na₂S₂O₃ (10 mL), and the mixture was extracted with EtOAc (2 × 15 mL). The organic layer was washed with H₂O, dried (Na₂SO₄), and concentrated in vacuo. The residue was purified by column chromatography (silica gel, EtOAc–PE).(E)-2-Iodo-2-phenylvinyl 4-Methoxyphenyl Sulfone (7c)Yellow oil; yield: 35.9 mg (45%). ¹H NMR (400 MHz, CDCl₃): δ = 7.48 (d, J = 4.0 Hz, 2 H), 7.37 (s, 1 H), 7.30–7.22 (m, 5 H), 6.84 (d, J = 4.0 Hz, 2 H), 3.85 (s, 3 H). 13C NMR (100 MHz, CDCl₃): δ = 163.55, 141.4, 132.5, 132.1, 131.0, 129.9, 129.0, 128.5, 127.9, 114.6, 55.7. HRMS (ESI): m/z [M + NH₄]⁺ calcd for C₁₅H₁₇INO₃S: 417.9968; found: 417.9963.