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Synlett 2016; 27(13): 2003-2008
DOI: 10.1055/s-0035-1561667
letter
© Georg Thieme Verlag Stuttgart · New York

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

Dingyi Wang
College of Chemistry, Nanchang University, Nanchang, Jiangxi 330031, P. R. of China   Email: senlin@ncu.edu.cn   Email: smguo@ncu.edu.cn
,
Rongxing Zhang
College of Chemistry, Nanchang University, Nanchang, Jiangxi 330031, P. R. of China   Email: senlin@ncu.edu.cn   Email: smguo@ncu.edu.cn
,
Sen Lin*
College of Chemistry, Nanchang University, Nanchang, Jiangxi 330031, P. R. of China   Email: senlin@ncu.edu.cn   Email: smguo@ncu.edu.cn
,
Zhaohua Yan
College of Chemistry, Nanchang University, Nanchang, Jiangxi 330031, P. R. of China   Email: senlin@ncu.edu.cn   Email: smguo@ncu.edu.cn
,
Shengmei Guo*
College of Chemistry, Nanchang University, Nanchang, Jiangxi 330031, P. R. of China   Email: senlin@ncu.edu.cn   Email: smguo@ncu.edu.cn
› Author Affiliations
Further Information

Publication History

Received: 22 April 2016

Accepted after revision: 15 May 2016

Publication Date:
14 June 2016 (online)

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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.