Citation: Xu Zheng, Zhou Bingwei, Jin Hongwei, Liu Yunkui. K₂S₂O₈/H₂O/NaOTf System-Promoted Schmidt Rearrangement Reaction of Vinyl Azides[J]. Chinese Journal of Organic Chemistry, ;2018, 38(7): 1823-1828. doi: 10.6023/cjoc201801025 shu

K₂S₂O₈/H₂O/NaOTf System-Promoted Schmidt Rearrangement Reaction of Vinyl Azides

State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014

Corresponding author: Liu Yunkui, ykuiliu@zjut.edu.cn
Received Date: 18 January 2018
Revised Date: 19 March 2018
Available Online: 4 July 2018
Fund Project: the National Natural Science Foundation of China 21772176the National Natural Science Foundation of China 21372201Project supported by the National Natural Science Foundation of China (Nos. 21772176, 21372201), the Opening Foundation of Zhejiang Key Course of Chemical Engineering and Technology, Zhejiang University of Technology

Figures(3)

Under neutral reaction conditions, sodium triflate promotes the radical reaction of potassium persulfate with water to yield a proton which induces Schmidt rearrangement of alkenyl azides. A variety of substituted acetanilide compounds were synthesized in one step. To obtain the optimal reaction conditions, an arrange of reaction parameters such as radical initiator, solvent, temperature, and reaction time have been screened. This reaction features an easy accessibility of starting materials, simple operation, broad substrate scope and so on. We finally proposed the plausible mechanism based on the mechanistic studies and previous literature.
- vinyl azides,
- acetanilides,
- radical reaction,
- Schmidt rearrangement
1. [1]
  (a) Sana, S. ; Rajanna, K. C. ; Reddy, K. R. ; Bhooshan, M. ; Venkateswarlu, M. ; Kumar, M. S. ; Uppalaiah, K. Green Sustainable Chem. 2012, 2, 97.
  (b) Sana, S. ; Rajanna, K. C. ; Ali, M. M. ; Saiprakash, P. K. Chem. Lett. 2000, 48.
2. [2]
  Sultane, P. R.; Mete, T. B.; Bhat, R. G. Org. Biomol. Chem. 2014, 12, 261. doi: 10.1039/C3OB41971A
3. [3]
  Li, Y.; Zhou, Y.-X.; Ma, X.; Jiang, H.-L. Chem. Commun. 2016, 52, 4199. doi: 10.1039/C6CC00011H
4. [4]
  Wrobleski, A.; Coombs, T. C.; Huh, C. W.; Li, S.-W.; Aubé, J. Org. React. 2012, 78, 1.
5. [5]
  (a) Schmidt, K. F. Angew. Chem. 1923, 36, 511.
  (b) Schmidt, K. F. Ber. 1924, 57, 704.
6. [6]
  Motiwala, H. F.; Fehl, C.; Li, S.-W.; Hirt, E.; Porubsky, P.; Aubé, J. J. Am. Chem. Soc. 2013, 135, 9000. doi: 10.1021/ja402848c
7. [7]
  (a) Insuasty, D. ; Robledo, S. M. ; Velez, I. D. ; Cuervo, P. ; Insuasty, B. ; Quiroga, J. ; Nogueras, M. ; Cobo, J. ; Abonia, R. Eur. J. Med. Chem. 2017, 141, 567.
  (b) Mor, M. ; Pahal, P. Pharm. Chem. 2016, 8, 296.
8. [8]
  Yu, C.-J.; Li, R.; Gu, P.-M. Tetrahedron Lett. 2016, 57, 3568. doi: 10.1016/j.tetlet.2016.06.124
9. [9]
  Chen, P.; Sun, C.-H.; Wang, Y.; Xue, Y.; Chen, C.; Shen, M.-H.; Xu, H.-D. Org. Lett. 2018, 20, 1643. doi: 10.1021/acs.orglett.8b00395
10. [10]
  (a) Chan, W. -H. ; Somal, G. K. ; Katz, C. E. ; Pei, H. -X. ; Zeng, Y. -B. ; Douglas, J. T. ; Aube, J. J. Org. Chem. 2009, 74, 7618.
  (b) Meyer, A. M. ; Katz, C. E. ; Li, S. -W. ; Velde, D. V. ; Aube, J. Org. Lett. 2010, 12, 1244.
11. [11]
  Song, X.-R.; Qiu, Y.-F.; Song, B.; Hao, X.-H.; Han, Y.-P.; Gao, P.; Liu, X.-Y.; Liang, Y.-M. J. Org. Chem. 2015, 80, 2263. doi: 10.1021/jo502761x
12. [12]
  Kim, C.; Kang, S.; Rhee, Y.-H. J. Org. Chem. 2014, 79, 11119. doi: 10.1021/jo502103p
13. [13]
  (a) Wang, Y. -F. ; Lonca, G. H. ; Runigo, M. ; Chiba, S. Org. Lett. 2014, 16, 4272.
  (b) Mackay, E. G. ; Studer, A. Chem. -Eur. J. 2016, 22, 1.
  (c) Sun, X. -Y. ; Yu, S. -Y. Chem. Commun. 2016, 52, 10898.
  (d) Yang, J. -C. ; Zhang, J. -J. ; Guo, L. -N. Org. Biomol. Chem. 2016, 14, 9806.
14. [14]
  (a) Hassner, A. ; Ferdinandi, E. S. ; Isbister, R. J. J. Am. Chem. Soc. 1970, 92, 1672.
  (b) Zhang, F. -L. ; Wang, Y. -F. ; Lonca, G. -H. ; Zhu, X. ; Chiba, S. Angew. Chem., Int. Ed. 2014, 53, 4390.
  (c) Zhang, F. -L. ; Zhu, X. ; Chiba, S. Org. Lett. 2015, 17, 3138.
15. [15]
  (a) Lu, S. -C. ; Gong, Y. -L. ; Zhou, D. -M. J. Org. Chem. 2015, 80, 9336.
  (b) Kianmehr, E. ; Faghih, N. ; Karaji, S. ; Lomedasht, Y. A. ; Khan, K. M. J. Organomet. Chem. 2016, 801, 10.
  (c) Yadav, A. K. ; Yadav, L. S. Tetrahedron Lett. 2016, 57, 1489.
16. [16]
  Zhang, J.; Chen, M.-Y.; Zhu, L. RSC Adv. 2016, 6, 758. doi: 10.1039/C5RA22457H
17. [17]
  Gaydou, M.; Echavarren, A. M. Angew. Chem., Int. Ed. 2013, 52, 13468, and references cited therein. doi: 10.1002/anie.201308076
18. [18]
  Wang, Y.-F.; Toh, K. K.; Lee, J.-Y.; Chiba, S. Angew. Chem., Int. Ed. 2011, 50, 5927, and references cited therein. doi: 10.1002/anie.v50.26
19. [19]
20. [20]
  Yang, S.-D.; Li, B.-J.; Wan, X.-B.; Shi, Z.-J. J. Am. Chem. Soc. 2007, 129, 6066. doi: 10.1021/ja070767s
21. [21]
  Ernest, W.; Barnett, B. F. J. Am. Chem. Soc. 1960, 82, 4671. doi: 10.1021/ja01502a055
22. [22]
  Peter, T. W. C.; Zheng, N.; Buchwald, S. L. J. Am. Chem. Soc. 2005, 127, 14560. doi: 10.1021/ja055353i
23. [23]
  H Xi, J.; Dong, Q.-L.; Liu, G.-S.; Wang, S.-Z.; Chen, L.; Yao, Z.-J. Synlett 2010, 1674.
24. [24]
  Fuson, R. C.; Talbom, R. L. J. Org. Chem. 1961, 26, 2674. doi: 10.1021/jo01066a016
25. [25]
  Antonchick, A. P.; Samanta, R.; Kulikov, K.; Lategahn, J. Angew. Chem., Int. Ed. 2011, 50, 8605. doi: 10.1002/anie.201102984
26. [26]
  Tsukamoto, H.; Suzuki, R.; Kondo, Y. J. Comb. Chem. 2006, 8, 289. doi: 10.1021/cc0600066
27. [27]
  Cho, G.-Y.; Remy, P.; Jansson, J.; Moessner, C.; Bolm, C. Org. Lett. 2004, 6, 3293. doi: 10.1021/ol048806h
28. [28]
  Fors, B. P.; Dooleweerdt, K.; Zeng, Q.-L.; Buchwald, S. L. Tetrahedron 2009, 65, 6576. doi: 10.1016/j.tet.2009.04.096
29. [29]
  Bedford, R. B.; Haddow, M. F.; Mitchell, C. J.; Webster, R. L. Angew. Chem., Int. Ed. 2011, 50, 5524. doi: 10.1002/anie.201101606
30. [30]
  Chen, C.-T.; Kuo, J.-H.; Pawar, V. D.; Munot, Y. S.; Weng, S.-S.; Ku, C.-H.; Liu, C.-Y. J. Org. Chem. 2005, 70, 1188. doi: 10.1021/jo048363v
31. [31]
  Epishina, M. A.; Kuliov, A. S.; Ignatev, N. V.; Schuite, M.; Makhova, N. N. Mendeleev Commun. 2010, 20, 335. doi: 10.1016/j.mencom.2010.11.011
32. [32]
  Taylor, E. J.; Jones, M. D.; Williams, J. M. J.; Bull, S. D. J. Org. Chem. 2012, 77, 2808. doi: 10.1021/jo202647f
33. [33]
  Huang X.-H.; Anderson, K. W.; Zim D.; Jiang, L.; Klapars, A.; Buchwald, S. L. J. Am. Chem. Soc. 2003, 125, 6653. doi: 10.1021/ja035483w
34. [34]
  Kajihara, K.; Arisawa, M.; Shuto, S. J. Org. Chem. 2008, 73, 9494. doi: 10.1021/jo801915c
35. [35]
  Cam-Van, N. T.; Diep, B. K.; Buu-Hoi, N. P. Tetrahedron 1964, 20, 2195. doi: 10.1016/S0040-4020(01)97604-5
36. [36]
  Antonow, D.; Marrafa, T.; Dawood, I.; Ahmed, T.; Haque, M. R.; Thurston, D. E.; Zinzalla, G. Chem. Commun. 2010, 46, 2289. doi: 10.1039/b924333j
37. [37]
  Sykulski, J. Acta Pol. Pharm. 1963, 20, 131.
38. [38]
  Liu, H.; Wang, X.-M.; Gu, Y.-H.; Org. Biomol. Chem. 2011, 9, 1614. doi: 10.1039/c0ob00749h
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K₂S₂O₈/H₂O/NaOTf System-Promoted Schmidt Rearrangement Reaction of Vinyl Azides