Citation: Taimin Wang, Xuecheng Zhu, Qingqing Tao, Wei Xu, Haiyan Sun, Ping Wu, Bin Cheng, Hongbin Zhai. Synthesis of tetrasubstituted thiophenes from pyridinium 1, 4-zwitterionic thiolates and modified activated alkynes[J]. Chinese Chemical Letters, ;2021, 32(12): 3972-3975. doi: 10.1016/j.cclet.2021.04.021 shu

Synthesis of tetrasubstituted thiophenes from pyridinium 1, 4-zwitterionic thiolates and modified activated alkynes

Taimin Wang ^{a, *,} ,
Xuecheng Zhu ^a ,
Qingqing Tao ^a ,
Wei Xu ^a ,
Haiyan Sun ^a ,
Ping Wu ^c ,
Bin Cheng ^{a, *,} ,
Hongbin Zhai ^{a, b, *,}

a.
Institute of Marine Biomedicine/Hoffmann Institute of Advanced Materials, Shenzhen Polytechnic, Shenzhen 518055, China
b.
State Key Laboratory of Chemical Oncogenomics, Shenzhen Engineering Laboratory of Nano Drug Slow-Release, Peking University Shenzhen Graduate School, Shenzhen 518055, China
c.
Key Laboratory of Coordination Chemistry and Functional Materials in Universities of Shandong, Dezhou College, Dezhou 253023, China

wangtm@szpt.edu.cn

chengbin@szpt.edu.cn

zhaihb@pkusz.edu.cn

Received Date: 25 January 2021
Revised Date: 9 April 2021
Accepted Date: 12 April 2021
Available Online: 18 April 2021

Figures(4)

Pyridinium 1, 4-zwitterionic thiolates were applied to a formal [3 + 2] annulation reaction with modified activated alkynes, affording various tetrasubstituted thiophenes with aryl, alkenyl, alkyl or silyl group at the special position. The structural modification of alkyne substrates enabled the synthesis of diverse thiophenes to be achieved using the pyridinium 1, 4-zwitterionic thiolates as the sulfur-containing building blocks. This approach is metal-free and catalyst-free.
- 1, 4-Zwitterionic thiolate,
- Activated alkyne,
- Formal [3 + 2],
- Thiophene,
- Metal-free,
- Catalyst-free
1. [1]
  L. Moafi, S. Ahadi, H.R. Khavasi, A. Bazgir, Synthesis (Mass) (2011) 1399–1402.
2. [2]
  (a) B. Cheng, Y. Li, T. Wang, et al., Chem. Commun. 55 (2019) 14606–14608;
  (b) B. Cheng, X. Duan, Y. Li, et al., Eur. J. Org. Chem. (2020) 1896–1906;
  (c) S. Zhai, X. Zhang, B. Cheng, et al., Chem. Commun. 56 (2020) 3085–3088;
  (d) B. Cheng, B. Bao, W. Xu, et al., Org. Biomol. Chem. 18 (2020) 2949–2955;
  (e) B. Cheng, Y. Li, T. Wang, et al., J. Org. Chem. 85 (2020) 6794–6802;
  (f) B. Cheng, X. Zhang, Y. Li, et al., Chem. Commun. 56 (2020) 8396–8399;
  (g) B. Cheng, Y. Li, X. Zhang, et al., Org. Lett. 22 (2020) 5817–5821;
  (h) B. Cheng, H. Li, S. Duan, et al., Org. Biomol. Chem. 18 (2020) 6253–6257;
  (i) B. Cheng, X. Zhang, H. Li, et al., Adv. Synth. Catal. 362 (2020) 4668–4672.
3. [3]
  (a) B. Godoi, R.F. Schumacher, G. Zeni, Chem. Rev. 111 (2011) 2937–2980;
  (b) K. Schaper, T.J.J. Müeller, Top. Curr. Chem. 376 (2018) 38;
  (c) F. Zamberlan, A. Fantinati, C. Trapella, Eur. J. Org. Chem. (2018) 3248–3264;
  (d) R. Mancuso, B. Gabriele, Molecules 19 (2014) 15687–15719;
  (e) J.A. Joule, Phosphorus Sulfur Silicon Relat. Elem. 188 (2013) 287–316;
  (f) S. Rajappa, A.R. Deshmunkh, Thiophenes and their benzo derivatives: reactivity, in: A.R. Katritzky, C.A. Ramsden, E.F.V. Scriven, R.J.K. Taylor (Eds. ), Comprehensive Heterocyclic Chemistry III, Elsevier Science, 2008, pp. 741–841;
  (g) S. Gronowitz, A.B. Hornfeldt, in: Thiophenes, Elsevier, Oxford, UK, 2004;
  (h) K.J. Hale, S. Manaviazar, Thiophenes, hydrothiophenes, benzothiophenes, and related compounds, in: M. Sainsbury (Ed. ), Second Supplements to the 2nd Edition of Rodd's Chemistry of Carbon Compounds, Elsevier, 2008. Vol. IV, Part A, 337-456;
  (i) L. Chen, H. Min, W. Zeng, et al., Org. Lett. 20 (2018) 7392–7395;
  (j) P. Fricero, L. Bialy, W. Czechtizky, M. Méndez, J.P.A. Harrity, Org. Lett. 20 (2018) 198–200;
  (k) M. Adib, S. Rajai-Daryasarei, R. Pashazadeh, et al., Eur. J. Org. Chem. (2018) 3001–3016;
  (l) J.K. Kim, H.J. Lim, K.C. Jeong, S.J. Park, Beilstein. J. Org. Chem. 14 (2018) 243–252;
  (m) D. Kurandina, V. Gevorgyan, Org. Lett. 18 (2016) 1804–1807;
  (n) S.N. Sahu, M.K. Gupta, S. Singh, et al., RSC Adv 5 (2015) 36979–36986;
  (o) A. Acharya, G. Parameshwarappa, S. Bonagiri, H. Ila, J. Org. Chem. 80 (2015) 414–427;
  (p) Z. Wang, Z. Qu, F. Xiao, H. Huang, G.J. Deng, Adv. Synth. Catal. 360 (2018) 796–800;
  (q) L.S. Ge, Z.L. Wang, X.L. An, X. Luo, W.P. Deng, Org. Biomol. Chem. 12 (2014) 8473–8479;
  (r) M. Adib, S. Rajai-Daryasarei, R. Pashazadeh, M. Jahani, M. Amanlou, Synlett 29 (2018) 1583–1588;
  (s) G. Bharathiraja, G. Sathishkannan, T. Punniyamurthy, J. Org. Chem. 81 (2016) 2670–2674.
4. [4]
  (a) K. Bozorov, L.F. Nie, J. Zhao, H.A. Aisa, Eur. J. Med. Chem. 140 (2017) 465–493;
  (b) M. Krátký, J. Vinsova, Curr. Top. Med. Chem. 16 (2016) 2921–2952;
  (c) D. Gramec, L.P. Mašič, M.S. Dolenc, Chem. Res. Toxicol. 27 (2014) 1344–1358;
  (d) K.K. Jha, S. Kumar, I. Tomer, R. Mishra, J. Pharm. Res. 5 (2012) 560–566.
5. [5]
  (a) C. Zhang, X. Zhu, Acc. Chem. Res. 50 (2017) 1342–1350;
  (b) G. Turkoglu, M.E. Cinar, T. Ozturk, Top. Curr. Chem. 375 (2017) 84;
  (c) S.C. Rasmussen, S.J. Evenson, C.B. McCausland, Chem. Commun. 51 (2015) 4528–4543;
  (d) A. Mishra, C.Q. Ma, P. Bäuerle, Chem. Rev. 109 (2009) 1141–1276.
6. [6]
  (a) B.H. Lipshutz, Chem. Rev. 86 (1986) 795–819;
  (b) G. Rassu, F. Zanardi, L. Battistini, G. Casiraghi, Chem. Soc. Rev. 29 (2000) 109–118;
  (c) C. Bianchini, A. Meli, Synlett 6 (1997) 643–649;
  (d) R. Kumar, R.K. Rej, S. Nanda, Tetrahedron Asymmetry 26 (2015) 751–759.
7. [7]
  (a) X. Jiang, in: Sulfur Chemistry, Springer, 2019;
  (b) M. Feng, B. Tang, S.H. Liang, X. Jiang, Curr. Top. Med. Chem. 16 (2016) 1200–1216;
  (c) N. Wang, P. Saidhareddy, X. Jiang, Nat. Prod. Rep. 37 (2020) 246–275.
8. [8]
  W.P. Ding, G.P. Zhang, Y.J. Jiang, et al., Org. Lett. 21 (2019) 6805–6810. doi: 10.1021/acs.orglett.9b02431
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