Citation: Zhang Shunji, Liu Huili. Sulfuric Acid Catalyzed Rapid Nucleophilic Substitution of Propargyl Alcohols[J]. Chinese Journal of Organic Chemistry, ;2020, 40(5): 1257-1265. doi: 10.6023/cjoc201911036 shu

Sulfuric Acid Catalyzed Rapid Nucleophilic Substitution of Propargyl Alcohols

Zhang Shunji ^, ,
Liu Huili

Department of Chemistry, Huaibei Normal University, Huaibei, Anhui 235000

Corresponding author: Zhang Shunji, sjzhang@chnu.edu.cn
Received Date: 27 November 2019
Revised Date: 6 January 2020
Available Online: 21 January 2020

Figures(1)

Sulfuric acid efficiently catalyzes the direct substitution of the hydroxyl group of propargylic alcohols with a variety of C- and O-based nucleophiles to aid C-C and C-O bond formation. The reactions can be performed in an undried solvent under air atmosphere to obtain the desired products in good yields. In most cases, the reaction proceeds to completion in 1 min at room temperature.
- sulfuric acid,
- catalyzed,
- propargyl alcohols,
- nucleophilic substitution
1. [1]
2. [2]
  (a) Georgy, M.; Boucard, V.; Campagne, J. J. Am. Chem. Soc. 2005, 127, 14180.
  (b) Trost, B. Acc. Chem. Res. 2002, 35, 695.
  (c) Georgy, M.; Boucard, V.; Campagne, J. J. Am. Chem. Soc. 2005, 127, 14180.
  (d) Emer, E.; Sinisi, R.; Capdevila, M. G.; Petruzziello, D.; Vincentiis, F. D.; Cozzi, P. G. Eur. J. Org. Chem. 2011, 647.
3. [3]
  (a) Nicholas, K. M.; Mulvaney, M.; Bayer, M. J. Am. Chem. Soc. 1980, 102, 2508.
  (b) Nicholas, K. M. Acc. Chem. Res. 1987, 20, 207.
  (c) Berge, J.; Claridge, S.; Mann, A.; Muller, C.; Tyrrell, E. Tetrahedron Lett. 1997, 38, 685.
  (d) Kuhn, O.; Rau, D.; Mayr, H. J. Am. Chem. Soc. 1998, 120, 900.
  (e) Montana, A. M.; Fernandez, D. Tetrahedron Lett. 1999, 40, 6499.
  (f) Teobald, B. J. Tetrahedron 2002, 58, 4133.
4. [4]
  (a) Sherry, B. D.; Radosevich, A. T.; Toste, F. D. J. Am. Chem. Soc. 2003, 125, 15760.
  (b) Kennedy-Smith, J. J.; Young, L. A.; Toste, F. D. Org. Lett. 2004, 6, 1325.
  (c) Ohri, R. V.; Radosevich, A. T.; Hrovat, K. J.; Musich, C.; Huang, D.; Holman, T. R. Org. Lett. 2005, 7, 2501.
5. [5]
  (a) Nishibayashi, Y.; Wakiji, I.; Hidai, M. J. Am. Chem. Soc. 2000, 122, 11019.
  (b) Nishibayashi, Y.; Wakiji, I.; Ishii, Y.; Uemura, S.; Hidai, M. J. Am. Chem. Soc. 2001, 123, 3393.
  (c) Nishibayashi, Y.; Yoshikawa, M.; Inada, Y.; Hidai, M.; Uemura, S. J. Am. Chem. Soc. 2002, 124, 11846.
  (d) Inada, Y.; Nishibayashi, Y.; Hidai, M.; Uemura, S. J. Am. Chem. Soc. 2002, 124, 15172.
  (e) Nishibayashi, Y.; Yoshikawa, M.; Inada, Y.; Hidai, M.; Uemura, S. J. Am. Chem. Soc. 2002, 14, 11846.
  (f) Nishibayashi, Y.; Inada, Y.; Hidai, M.; Uemura, S. J. Am. Chem. Soc. 2003, 125, 6060.
  (g) Nishibayashi, Y.; Yoshikawa, M.; Inada, Y.; Hidai, M.; Uemura, S. Angew. Chem., Int. Ed. 2003, 42, 1495.
  (h) Cadierno, V.; Diez, J.; Garcia-Garrido, S. E.; Gimerno, J. Chem. Commun. 2004, 2716.
  (i) Fischmeister, C.; Toupet, L.; Dixneuf, P. H. New J. Chem. 2005, 29, 765.
  (j) Nishibayashi, Y.; Milton, M. D.; Inada, Y.; Yoshikawa, M.; Wakiji, I.; Hidai, M.; Uemura, S. Chem.-Eur. J. 2005, 11, 1433.
  (k) Nishibayashi, Y.; Uemura, S. Curr. Org. Chem. 2006, 10, 135.
  (l) Bustelo, E.; Dixneuf, P. H. Adv. Synth. Catal. 2007, 349, 933.
6. [6]
  (a) Zhan, Z.; Yang, W.; Yang, R.; Yu, J.; Li, J.; Liu, H. Chem. Commun. 2006, 3352.
  (b) Jana, U.; Maiti, S.; Biswas, S. Tetrahedron Lett. 2007, 48, 7160.
  (c) Yan, W.; Wang, Q.; Chen, Y.; Petersen, J. L.; Shi, X. Org. Lett. 2010, 12, 3308.
  (d) Mantione, R. Bull. Soc. Chim. Fr. 1969, 4514.
  (e) Hayashi, M.; Inbushi, A.; Mukaiyama, T. Bull. Soc. Chem. Jpn. 1988, 61, 4037.
  (f) Shi, M.; Shouki, K.; Okamoto, Y.; Takamuku, S. J. Chem. Soc., Perkin Trans. 1 1990, 2443.
  (g) Burgess, K.; Jennings, L. D. J. Am. Chem. Soc. 1991, 6129.
7. [7]
  (a) Zhang, X.; Teo, W.; Chan, W. Org. Lett. 2009, 11, 4990.
  (b) Gohain, M.; Marais, C.; Bezuidenhoudt, B. C. Tetrahedron Lett. 2012, 53, 1048.
8. [8]
  (a) Sanz, R.; Martínez, A.; Álvarez-Gutiérrez, J.; Rodríguez, F. Eur. J. Org. Chem. 2006, 1383.
  (b) Sanz, R.; Miguel, D.; Martínez, A.; Álvarez-Gutiérrez, J.; Rodríguez, F. Org. Lett. 2007, 9, 727.
  (c) Sanz, R.; Miguel, D.; Martínez, A.; Gohain, M.; García-García, P.; Fernández-Rodríguez, M.; Álvarez, E.; Rodríguez, F. Eur. J. Org. Chem. 2010, 7027.
  (d) Gangadhararao, G.; Uruvakilli, A.; Kumara Swamy, K. C. Org. Lett. 2014, 16, 6060.
  (e) Zhang, X.; Teng, W.; Sally, T.; Wai, P.; Chan, H. J. Org. Chem. 2010, 75, 6290.
  (f) Wang T.; Chen X.; Chen L.; Zhan Z. Org. Lett. 2011, 13, 3324.
9. [9]
  Barreiro, E.; Vidal, A. S.; Tan, E.; Lau, S.; Sheppard, T. D.; González, S. D. Eur. J. Org. Chem. 2015, 7544.
10. [10]
  Savarimuthu, S. A.; Prakash, D. L.; Thomas, S. A. Tetrahedron Lett. 2014, 55, 3213. doi: 10.1016/j.tetlet.2014.02.086
11. [11]
  Yokosaka, T.; Shiga, N.; Nemoto, T.; Hamada, Y. J. Org. Chem. 2014, 79, 3866. doi: 10.1021/jo500308y
12. [12]
  Wang, L.; Xie, X.; Liu, Y. Org. Lett. 2012, 23, 5848.
13. [13]
  (a) Shaterian, H. R.; Yarahmadi, H.; Ghashang, M. Tetrahedron 2008, 64, 1263.
  (b) Murugan, K.; Chen, C. Tetrahedron Lett. 2011, 52, 5827.
14. [14]
  (a) Yadav, J. S.; Reddy, B. V. S.; Reddy, A. S. J. Mol. Catal. A: Chem. 2008, 280, 219.
  (b) Srihari, P.; Reddy, J. S. S.; Bhunia, D. C.; Mandal, S. S.; Yadav, J. S. Synth. Commun. 2008, 38, 1448.
  (c) Srihari, P.; Reddy, J. S. S.; Mandal, S. S.; Satyanarayana, K.; Yadav, J. S. Synthesis 2008, 1853.
  (d) Jang, S.; Kim, A. Y.; Seo, W. S.; Park, K. H. Nanoscale Res. Lett. 2015, 10, 2.
15. [15]
  Antonino, J. R. C.; Prez, A. L.; Corma, A. Angew. Chem., Int. Ed. 2015, 54, 5658.
16. [16]
  Yadav, J. S.; Reddy, B. V. S.; Narayanakumar, G. G. K. S.; Rao, K. V. R. Chem. Lett. 2007, 36, 942. doi: 10.1246/cl.2007.942
17. [17]
  Gujarathi, S.; Hendrickson, H. P.; Zheng, G. Tetrahedron Lett. 2013, 54, 3550. doi: 10.1016/j.tetlet.2013.04.120
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