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Synlett 2020; 31(17): 1720-1724
DOI: 10.1055/s-0040-1707249
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© Georg Thieme Verlag Stuttgart · New York

Electrochemical Synthesis of Vinyl Sulfones by Sulfonylation of Styrenes with a Catalytic Amount of Potassium Iodide

Pei-Long Wang
a   Key Laboratory of Green and Precise Synthetic Chemistry and Applications Ministry of Education, Department of Chemistry, Huaibei Normal University, Huaibei, Anhui 235000, P. R. of China   Email: gaohui20032@163.com   Email: pinhuali@mail.ustc.edu.cn
b   Information College, Huaibei Normal University, Huaibei, Anhui 235000, P. R. of China
,
Hui Gao∗
a   Key Laboratory of Green and Precise Synthetic Chemistry and Applications Ministry of Education, Department of Chemistry, Huaibei Normal University, Huaibei, Anhui 235000, P. R. of China   Email: gaohui20032@163.com   Email: pinhuali@mail.ustc.edu.cn
,
Zhi-Sheng Jiang
a   Key Laboratory of Green and Precise Synthetic Chemistry and Applications Ministry of Education, Department of Chemistry, Huaibei Normal University, Huaibei, Anhui 235000, P. R. of China   Email: gaohui20032@163.com   Email: pinhuali@mail.ustc.edu.cn
,
Chao Li
a   Key Laboratory of Green and Precise Synthetic Chemistry and Applications Ministry of Education, Department of Chemistry, Huaibei Normal University, Huaibei, Anhui 235000, P. R. of China   Email: gaohui20032@163.com   Email: pinhuali@mail.ustc.edu.cn
,
Zhi-Ao Tian
a   Key Laboratory of Green and Precise Synthetic Chemistry and Applications Ministry of Education, Department of Chemistry, Huaibei Normal University, Huaibei, Anhui 235000, P. R. of China   Email: gaohui20032@163.com   Email: pinhuali@mail.ustc.edu.cn
,
Pin-Hua Li∗
a   Key Laboratory of Green and Precise Synthetic Chemistry and Applications Ministry of Education, Department of Chemistry, Huaibei Normal University, Huaibei, Anhui 235000, P. R. of China   Email: gaohui20032@163.com   Email: pinhuali@mail.ustc.edu.cn
› Author AffiliationsWe gratefully thank the Anhui Provincial Natural Science Foundation (No. 1808085QB29) and Key Project of Provincial Natural Science Research Foundation of Anhui Universities, China (No. KJ2018A0675, KJ2018A0389) for financial support.
Further Information

Publication History

Received: 21 June 2020

Accepted after revision: 19 July 2020

Publication Date:
26 August 2020 (online)

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Abstract

An electrochemical sulfonylation reaction of styrenes was developed in which sodium arylsulfinates were used as sulfonylating reagents, a catalytic amount of KI was used as a redox mediator, and Bu4NBF4 was used as the electrolyte. In addition to various styrenes, sodium arylsulfinates with either electron-donating or electron-withdrawing groups were tolerated.

Key words

electrochemical synthesis - vinyl sulfones - sulfonylation - styrenes - sodium sulfinates

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1707249.
  • Supporting Information
 

  • References and Notes


      • For selected examples, see:
    • 1a Reddick JJ, Cheng J, Roush WR. Org. Lett. 2003; 5: 1967
      Article in Thieme ConnectPubMed
    • 1b Wang G, Mahesh U, Chen GY. J, Yao SQ. Org. Lett. 2003; 5: 737
      CrossrefPubMed
    • 1c Frankel BA, Bentley M, Kruger RG, McCafferty DG. J. Am. Chem. Soc. 2004; 126: 3404
      CrossrefPubMed
    • 1d Uttamchandani M, Liu K, Panicker RC, Yao SQ. Chem. Commun. 2007; 1518
      Article in Thieme ConnectPubMed
    • 1e Gordon CP, Griffith R, Keller PA. Med. Chem. (Sharjah, United Arab Emirates) 2007; 3: 199
      Crossref
    • 1f Meadows DC, Sanchez T, Neamati N, North TW, Gervay-Hague J. Bioorg. Med. Chem. 2007; 15: 1127
      CrossrefPubMed

      For selected examples, see:
    • 2a Ley SV, Lygo B, Wonnacott A. Tetrahedron Lett. 1985; 26: 535
      CrossrefPubMed
    • 2b Trost BM, Ghadiri MR. J. Am. Chem. Soc. 1986; 108: 1098
      Crossref
    • 2c Back TG, Proudfoot JR, Djerassi C. Tetrahedron Lett. 1986; 27: 2187
      Crossref
    • 2d Virgili M, Belloch J, Mayano A, Pericàs MA, Riera A. Tetrahedron Lett. 1991; 32: 4583
      Crossref
    • 2e Chen S.-H, Horvath RF, Joglar J, Fischer MJ, Danishefsky SJ. J. Org. Chem. 1991; 56: 5834
      Crossref
    • 2f Fotsch CH, Chamberlin AR. J. Org. Chem. 1991; 56: 4141
      Crossref
    • 2g Ibáñez PL, Nájera C. Tetrahedron Lett. 1993; 34: 2003
      Crossref
    • 2h Keck GE, Savin KA, Weglarz MA. J. Org. Chem. 1995; 60: 3194
      Crossref
    • 2i Nájera C, Yus M. Tetrahedron 1999; 55: 10547
      Crossref
    • 2j Ni L, Zheng XS, Somers PK, Hoong LK, Hill RR, Marino EM, Suen KL, Saxena U, Meng CQ. Bioorg. Med. Chem. Lett. 2003; 13: 745
      CrossrefPubMed
    • 2k Wardrop DJ, Fritz J. Org. Lett. 2006; 8: 3659
      CrossrefPubMed
    • 2l Das I, Pathak T. Org. Lett. 2006; 8: 1303
      CrossrefPubMed
    • 2m López-Pérez A, Robles-Machín R, Adrio J, Carretero JC. Angew. Chem. Int. Ed. 2007; 46: 9261
      CrossrefPubMed
    • 2n Clive DL. J, Li Z, Yu M. J. Org. Chem. 2007; 72: 5608
      CrossrefPubMed
    • 2o Noshi MN, El-awa A, Torres E, Fuchs PL. J. Am. Chem. Soc. 2007; 129: 11242
      CrossrefPubMed
    • 2p Zhu Q, Lu Y. Org. Lett. 2009; 11: 1721
      CrossrefPubMed
    • 2q Sulzer-Mossé S, Alexakis A, Mareda J, Bollot G, Bernardinelli G, Filinchuk Y. Chem. Eur. J. 2009; 15: 3204
      CrossrefPubMed
    • 2r Sun X, Yu F, Ye T, Liang X, Ye J. Chem. Eur. J. 2011; 17: 430
      CrossrefPubMed
    • 2s Nishimura T, Takiguchi Y, Hayashi T. J. Am. Chem. Soc. 2012; 134: 9086
      CrossrefPubMed
    • 3a Bian M, Xu F, Ma C. Synthesis 2007; 2951
    • 3b Huang F, Batey RA. Tetrahedron 2007; 63: 7667
      Crossref
    • 3c Liang S, Zhang R.-Y, Wang G, Chen S.-Y, Yu X.-Q. Eur. J. Org. Chem. 2013; 7050
    • 3d Rokade BV, Prabhu KR. J. Org. Chem. 2014; 79: 8110
      CrossrefPubMed
    • 3e Xu Y, Tang X, Hu W, Jiang H. Green Chem. 2014; 16: 3720
      Crossref
    • 3f Guo R, Gui Q, Wang D, Tan Z. Catal. Lett. 2014; 79: 1377
    • 3g Jiang Q, Xu B, Jia J, Zhao A, Zhao Y.-R, Li Y.-Y, He N.-N, Guo C.-C. J. Org. Chem. 2014; 79: 7372
      CrossrefPubMed
    • 3h Chen J, Mao J, Zheng Y, Rong D, Liu G, Yan H, Zhang C, Shi D. Tetrahedron 2015; 71: 5059
      Crossref
    • 3i Gao J, Lai J, Yuan G. RSC Adv. 2015; 5: 66723
      Crossref
    • 3j Nie G, Deng X, Lei X, Hu Q, Chen Y. RSC Adv. 2016; 6: 75277
      Crossref
    • 3k Xue N, Guo R, Tu X, Luo W, Deng W, Xiang J. Synlett 2016; 27: 2695
      Article in Thieme Connect
  • 4 Taniguchi N. Synlett 2011; 1308
    Article in Thieme Connect
  • 5 Gui Q, Han K, Liu Z, Su Z, He X, Jiang H, Tian B, Li Y. Org. Biomol. Chem. 2018; 16: 5748
    CrossrefPubMed
  • 6 Nair V, Augustine A, George TG, Nair LG. Tetrahedron Lett. 2001; 42: 6763
    Crossref
  • 7 Das B, Lingaiah M, Damodar K, Bhunia N. Synthesis 2011; 2941
    CrossrefPubMed
  • 8 Zhang N, Yang D, Wei W, Yuan L, Cao Y, Wang H. RSC Adv. 2015; 5: 37013
    Crossref
  • 9 Katrun P, Chiampanichayakul S, Korworapan K, Pohmakotr M, Reutrakul V, Jaipetch T, Kuhakarn C. Eur. J. Org. Chem. 2010; 5633

      • For selected books and reviews on electrochemical synthesis, see:
    • 10a Grimshaw J. Electrochemical Reactions and Mechanisms in Organic Chemistry. Elsevier; Amsterdam: 2000
      Google Scholar
    • 10b Organic Electrochemistry, 4th ed. Lund H, Hammerich O. Marcel Dekker; New York: 2001
      Google Scholar
    • 10c Sperry JB, Wright DL. Chem. Soc. Rev. 2006; 35: 605
      CrossrefPubMed
    • 10d Frontana-Uribe BA, Little RD, Ibanez JG, Palma A, Vasquez-Medrano R. Green Chem. 2010; 12: 2099
      Crossref
    • 10e Francke R, Little RD. Chem. Soc. Rev. 2014; 43: 2492
      CrossrefPubMed
    • 10f Fundamentals and Applications of Organic Electrochemistry: Synthesis, Materials, Devices. Fuchigami T, Inagi S, Atobe M. Wiley-VCH; Chichester: 2015
      Google Scholar
    • 10g Yan M, Kawamata Y, Baran PS. Chem. Rev. 2017; 117: 13230
      CrossrefPubMed
    • 10h Möhle S, Zirbes M, Rodrigo E, Gieshoff T, Wiebe A, Waldvogel SR. Angew. Chem. Int. Ed. 2018; 57: 6018
      CrossrefPubMed
    • 10i Kärkäs MD. Chem. Soc. Rev. 2018; 47: 5786
      CrossrefPubMed
    • 10j Moeller KD. Chem. Rev. 2018; 118: 4817
      CrossrefPubMed
    • 10k Wiebe A, Gieshoff T, Möhle S, Rodrigo E, Zirbes M, Waldvogel SR. Angew. Chem. Int. Ed. 2018; 57: 5594
      CrossrefPubMed
    • 10l Xiong P, Xu H.-C. Acc. Chem. Res. 2019; 52: 3339
      CrossrefPubMed
    • 10m Yuan Y, Lei A. Acc. Chem. Res. 2019; 52: 3309
      CrossrefPubMed
    • 10n Kingston C, Palkowitz MD, Takahira Y, Vantourout JC, Peters BK, Kawamata Y, Baran PS. Acc. Chem. Res. 2020; 53: 72
      CrossrefPubMed
  • 11 Qian P, Bi M, Su J, Zha Z, Wang Z. J. Org. Chem. 2016; 81: 4876
    CrossrefPubMed
  • 12 Luo Y.-C, Pan X.-J, Yuan G.-Q. Tetrahedron 2015; 71: 2119
    Crossref
  • 13 Electrochemical Sulfonylation of Styrenes 3a–w; General Procedure An undivided cell equipped with a Pt anode (1.0 × 1.0 × 0.02 cm) and a graphite rod cathode was charged with the appropriate sodium arylsulfinate (2 mmol), KI (0.5 mmol), and Bu4NBF4 (1 mmol). The vessel was evacuated and backfilled with N2 (×3). The appropriate styrene (1 mmol), DMSO (3 mL), and AcOH (3 mL) were added sequentially from a syringe. Electrolysis was carried out at a constant current of 12 mA at 50 °C for 10 h. The mixture was then cooled to rt and filtered through a plug of silica, eluting with EtOAc. The filtrate was washed with H2O (×3) and extracted with EtOAc. The organic layer was washed with brine, dried (Na2SO4), and evaporated to dryness under reduced pressure. The residue was purified by column chromatography [silica gel, PE–EtOAc (5:1)].
  • 14 (E)-2-Phenylvinyl 4-Tolyl Sulfone (3a) White solid; yield: 209.4 mg (81%); mp 119–120 °C. 1H NMR (600 MHz, CDCl3): δ = 7.83 (d, J = 8.3 Hz, 2 H), 7.66 (d, J = 15.4 Hz, 1 H), 7.48–7.47 (m, 2 H), 7.42–7.34 (m, 5 H), 6.85 (d, J = 15.4 Hz, 1 H), 2.43 (s, 3 H). 13C NMR (151 MHz, CDCl3): δ = 144.5, 142.1, 137.8, 132.6, 131.2, 130.1, 129.2, 128.7, 127.8, 127.7, 21.8. HRMS (ESI): m/z [M + H]+ calcd for C15H15O2S: 259.0787; found: 259.0789. (E)-4-(2-Tosylvinyl)benzonitrile (3h) White solid; yield: 234.6 mg (83%); mp 125–127 °C. 1H NMR (600 MHz, CDCl3): δ = 7.83 (d, J = 8.3 Hz, 2 H), 7.69 (d, J = 8.3 Hz, 2 H), 7.65 (d, J = 15.5 Hz, 1 H), 7.58 (d, J = 8.3 Hz, 2 H), 7.37 (d, J = 8.0 Hz, 2 H), 6.96 (dd, J = 15.4, 0.8 Hz, 1 H), 2.45 (s, 3 H). 13C NMR (151 MHz, CDCl3): δ = 145.1, 139.4, 136.9, 136.8, 132.9, 131.4, 130.3, 129.0, 128.1, 118.2, 114.3, 21.8. HRMS (ESI): m/z [M + H]+ calcd for C16H14NO2S: 284.0740; found: 284.0738. (E)-2-(2-Naphthyl)vinyl 4-Tolyl Sulfone (3k) Yellow solid; yield: 246.9 mg (80%); mp 160–162 °C. 1H NMR (400 MHz, CDCl3): δ = 7.91–7.79 (m, 7 H), 7.54–7.49 (m, 3 H), 7.34 (d, J = 7.9 Hz, 2 H), 6.96 (d, J = 15.4 Hz, 1 H), 2.42 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 144.5, 142.1, 137.9, 134.5, 133.2, 131.0, 130.1, 130.0, 129.0, 128.8, 127.9, 127.8, 127.7, 127.1, 123.5, 21.7. HRMS (ESI): m/z [M + H]+ calcd for C19H17O2S: 309.0944; found: 309.0948. 2-Chlorophenyl (E)-2-Phenylvinyl Sulfone (3v) White solid; yield: 247.8 mg (89%); mp 93–94 °C. 1H NMR (400 MHz, CDCl3): δ = 8.22 (d, J = 7.7 Hz, 1 H), 7.77 (d, J = 15.4 Hz, 1 H), 7.57–7.39 (m, 8 H), 7.08 (d, J = 15.4 Hz, 1 H). 13C NMR (101 MHz, CDCl3): δ = 145.4, 138.2, 134.6, 132.9, 132.4, 132.0, 131.5, 130.8, 129.2, 128.8, 127.6, 125.3. HRMS (ESI): m/z [M + H]+ calcd for C14H15ClNO2S: 296.0507; found: 296.0513 2-Phenylprop-2-en-1-yl 4-Tolyl Sulfone (3w) White solid; yield: 197.9 mg (73%); mp 97–98 °C. 1H NMR (400 MHz, CDCl3): δ = 7.67–7.64 (m, 2 H), 7.29–7.21 (m, 7 H), 5.59 (s, 1 H), 5.21 (s, 1 H), 4.25 (s, 2 H), 2.39 (s, 3 H). 13C NMR (151 MHz, CDCl3): δ = 144.7, 139.0, 136.7, 135.5, 129.6, 128.8, 128.5, 128.0, 126.3, 121.9, 62.2, 21.7. HRMS (ESI): m/z [M + H]+ calcd for C16H16NaO2S: 295.0763; found: 295.0765.