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

Pei-Long Wang; Hui Gao; Zhi-Sheng Jiang; Chao Li; Zhi-Ao Tian; Pin-Hua Li

doi:10.1055/s-0040-1707249

Synlett, Inhaltsverzeichnis

Synlett 2020; 31(17): 1720-1724
DOI: 10.1055/s-0040-1707249

letter

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

Pei-Long Wang

^aKey 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

^bInformation College, Huaibei Normal University, Huaibei, Anhui 235000, P. R. of China

,

Hui Gao∗

^aKey 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

^aKey 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

^aKey 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

^aKey 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∗

^aKey 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

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

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

Volltext

Referenzen

References and Notes

For selected examples, see:

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

For selected examples, see:

2a Ley SV, Lygo B, Wonnacott A. Tetrahedron Lett. 1985; 26: 535
2b Trost BM, Ghadiri MR. J. Am. Chem. Soc. 1986; 108: 1098
2c Back TG, Proudfoot JR, Djerassi C. Tetrahedron Lett. 1986; 27: 2187
2d Virgili M, Belloch J, Mayano A, Pericàs MA, Riera A. Tetrahedron Lett. 1991; 32: 4583
2e Chen S.-H, Horvath RF, Joglar J, Fischer MJ, Danishefsky SJ. J. Org. Chem. 1991; 56: 5834
2f Fotsch CH, Chamberlin AR. J. Org. Chem. 1991; 56: 4141
2g Ibáñez PL, Nájera C. Tetrahedron Lett. 1993; 34: 2003
2h Keck GE, Savin KA, Weglarz MA. J. Org. Chem. 1995; 60: 3194
2i Nájera C, Yus M. Tetrahedron 1999; 55: 10547
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
2k Wardrop DJ, Fritz J. Org. Lett. 2006; 8: 3659
2l Das I, Pathak T. Org. Lett. 2006; 8: 1303
2m López-Pérez A, Robles-Machín R, Adrio J, Carretero JC. Angew. Chem. Int. Ed. 2007; 46: 9261
2n Clive DL. J, Li Z, Yu M. J. Org. Chem. 2007; 72: 5608
2o Noshi MN, El-awa A, Torres E, Fuchs PL. J. Am. Chem. Soc. 2007; 129: 11242
2p Zhu Q, Lu Y. Org. Lett. 2009; 11: 1721
2q Sulzer-Mossé S, Alexakis A, Mareda J, Bollot G, Bernardinelli G, Filinchuk Y. Chem. Eur. J. 2009; 15: 3204
2r Sun X, Yu F, Ye T, Liang X, Ye J. Chem. Eur. J. 2011; 17: 430
2s Nishimura T, Takiguchi Y, Hayashi T. J. Am. Chem. Soc. 2012; 134: 9086

3a Bian M, Xu F, Ma C. Synthesis 2007; 2951
3b Huang F, Batey RA. Tetrahedron 2007; 63: 7667
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
3e Xu Y, Tang X, Hu W, Jiang H. Green Chem. 2014; 16: 3720
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
3h Chen J, Mao J, Zheng Y, Rong D, Liu G, Yan H, Zhang C, Shi D. Tetrahedron 2015; 71: 5059
3i Gao J, Lai J, Yuan G. RSC Adv. 2015; 5: 66723
3j Nie G, Deng X, Lei X, Hu Q, Chen Y. RSC Adv. 2016; 6: 75277
3k Xue N, Guo R, Tu X, Luo W, Deng W, Xiang J. Synlett 2016; 27: 2695

4 Taniguchi N. Synlett 2011; 1308
5 Gui Q, Han K, Liu Z, Su Z, He X, Jiang H, Tian B, Li Y. Org. Biomol. Chem. 2018; 16: 5748
6 Nair V, Augustine A, George TG, Nair LG. Tetrahedron Lett. 2001; 42: 6763
7 Das B, Lingaiah M, Damodar K, Bhunia N. Synthesis 2011; 2941
8 Zhang N, Yang D, Wei W, Yuan L, Cao Y, Wang H. RSC Adv. 2015; 5: 37013
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
10b Organic Electrochemistry, 4th ed. Lund H, Hammerich O. Marcel Dekker; New York: 2001
10c Sperry JB, Wright DL. Chem. Soc. Rev. 2006; 35: 605
10d Frontana-Uribe BA, Little RD, Ibanez JG, Palma A, Vasquez-Medrano R. Green Chem. 2010; 12: 2099
10e Francke R, Little RD. Chem. Soc. Rev. 2014; 43: 2492
10f Fundamentals and Applications of Organic Electrochemistry: Synthesis, Materials, Devices. Fuchigami T, Inagi S, Atobe M. Wiley-VCH; Chichester: 2015
10g Yan M, Kawamata Y, Baran PS. Chem. Rev. 2017; 117: 13230
10h Möhle S, Zirbes M, Rodrigo E, Gieshoff T, Wiebe A, Waldvogel SR. Angew. Chem. Int. Ed. 2018; 57: 6018
10i Kärkäs MD. Chem. Soc. Rev. 2018; 47: 5786
10j Moeller KD. Chem. Rev. 2018; 118: 4817
10k Wiebe A, Gieshoff T, Möhle S, Rodrigo E, Zirbes M, Waldvogel SR. Angew. Chem. Int. Ed. 2018; 57: 5594
10l Xiong P, Xu H.-C. Acc. Chem. Res. 2019; 52: 3339
10m Yuan Y, Lei A. Acc. Chem. Res. 2019; 52: 3309
10n Kingston C, Palkowitz MD, Takahira Y, Vantourout JC, Peters BK, Kawamata Y, Baran PS. Acc. Chem. Res. 2020; 53: 72

11 Qian P, Bi M, Su J, Zha Z, Wang Z. J. Org. Chem. 2016; 81: 4876
12 Luo Y.-C, Pan X.-J, Yuan G.-Q. Tetrahedron 2015; 71: 2119
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.

Zusatzmaterial

Supporting Information