Citation: Hu Juanjuan, Huang Yangen, Xu Xiuhua, Qing Fengling. Copper-Catalyzed Hydroxytrifluoromethylthiolation of Arylpropynones[J]. Chinese Journal of Organic Chemistry, ;2019, 39(1): 177-182. doi: 10.6023/cjoc201808041 shu

Copper-Catalyzed Hydroxytrifluoromethylthiolation of Arylpropynones

a.
Key Laboratory of Science and Technology of Eco-Textiles, Ministry of Education, College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620
b.
Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Corresponding author: Qing Fengling, flq@mai.sioc.ac.cn
Received Date: 30 August 2018
Revised Date: 23 October 2018
Available Online: 11 January 2018
Fund Project: the Strategic Priority Research Program of the Chinese Academy of Sciences XDB20000000the National Natural Science Foundation of China 21421002the National Natural Science Foundation of China 21332010the Youth Innovation Promotion Association of the Chinese Academy of Sciences 2016234Project supported by the National Natural Science Foundation of China (Nos. 21332010, 21421002), the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB20000000), and the Youth Innovation Promotion Association of the Chinese Academy of Sciences (No. 2016234)

Figures(2)

Recently, the preparation of fluorinated compounds through difunctionalization strategies has become a hot research area in fluorine chemistry. In this work, a copper-catalyzed hydroxytrifluoromethylthiolation of arylpropynones for the synthesis of the corresponding trifluoromethylthiolated enols was developed. The copper salt and solvent are crucial to the yields of this reaction. Under optimized reaction conditions, a series of trifluoromethylthiolated enols were obtained in moderate to good yields.
- copper,
- trifluoromethylthiolation,
- hydroxylation,
- propynone,
- radical
1. [1]
2. [2]
  (a) Hansch, C.; Leo, A.; Unger, S. H.; Kim, K. H.; Nikaitani, D.; Lien, E. J. J. Med. Chem. 1973, 16, 1207.
  (b) Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165.
3. [3]
4. [4]
  (a) Sheng, J.; Li, S.; Wu, J. Chem. Commun. 2014, 50, 578.
  (b) Zhang, K.; Liu, J.-B.; Qing, F.-L. Chem. Commun. 2014, 50, 14157.
  (c) Zhu, L.; Wang, G.; Guo, Q.; Xu, Z.; Zhang, D.; Wang, R. Org. Lett. 2014, 16, 5390.
  (d) Yang, T.; Lu, L.; Shen, Q. Chem. Commun. 2015, 51, 5479.
  (e) Chen, D.-Q.; Gao, P.; Zhou, P.-X.; Song, X.-R.; Qiu, Y.-F.; Liu, X.-Y.; Liang, Y. M. Chem. Commun. 2015, 51, 6637.
  (f) Fuentes, N.; Kong, W.; Fernández-Sánchez, L.; Merino, E.; Nevado, C. J. Am. Chem. Soc. 2015, 137, 964.
  (g) Luo, J.; Zhu, Z.; Liu, Y.; Zhao, X. Org. Lett. 2015, 17, 3620.
  (h) Xu, C.; Shen, Q. Org. Lett. 2015, 17, 4561.
  (i) Liu, X.; An, R.; Zhang, X.; Luo, J.; Zhao, X. Angew. Chem., Int. Ed. 2016, 55, 5846.
  (j) Zhang, P.; Li, M.; Xue, X.-S.; Xu, C.; Zhao, Q.; Liu, Y.; Wang, H.; Guo, Y.; Lu, L.; Shen, Q. J. Org. Chem. 2016, 81, 7486.
  (k) Jin, D.-P.; Gao, P.; Chen, D.-Q.; Chen, S.; Wang, J.; Liu, X.-Y.; Liang, Y.-M. Org. Lett. 2016, 18, 3486.
  (l) Luo, J.; Liu, Y.; Zhao, X. Org. Lett. 2017, 19, 3434.
  (m) Pan, S.; Huang, Y.; Xu, X.-H.; Qing, F.-L. Org. Lett. 2017, 19, 4624.
  (n) Liu, X.; Liang, Y.; Ji, J.; Luo, J.; Zhao, X. J. Am. Chem. Soc. 2018, 140, 4782.
  (o) Xiao, Z.; Liu, Y.; Zheng, L.; Liu, C.; Guo, Y.; Chen, Q.-Y. J. Org. Chem. 2018, 83, 5836.
  (p) Xi, C.-C.; Chen, Z.-M.; Zhang, S.-Y.; Tu, Y.-Q. Org. Lett. 2018, 20, 4227.
5. [5]
  Wu, W.; Dai, W.; Ji, X.; Cao, S. Org. Lett. 2016, 18, 2918. doi: 10.1021/acs.orglett.6b01286
6. [6]
  (a) Guo, C.-H.; Chen, D.-Q.; Chen, S.; Liu, X.-Y. Adv. Synth. Catal. 2017, 359, 2901.
  (b) Li, H.; Liu, S.; Huang, Y.; Xu, X.-H.; Qing, F.-L. Chem. Commun. 2017, 53, 10136.
7. [7]
  (a) Tlili, A.; Alazet, S.; Glenadel, Q.; Billard, T. Chem.-Eur. J. 2016, 22, 10230.
  (b) Pan, S.; Li, H.; Huang, Y.; Xu, X.-H.; Qing, F.-L. Org. Lett. 2017, 19, 3247.
8. [8]
  Jiang, L.; Ding, T.; Yi, W.-B.; Zeng, X.; Zhang, W. Org. Lett. 2018, 20, 2236. doi: 10.1021/acs.orglett.8b00581
9. [9]
  (a) Ferry, A.; Billard, T.; Langlois, B. R.; Bacqué, E. Angew. Chem., Int. Ed. 2009, 48, 8551.
  (b) Wu, J.-J.; Xu, J.; Zhao, X. Chem.-Eur. J. 2016, 22, 15265.
10. [10]
  (a) Yang, Y.; Jiang, X.-L.; Qing, F.-L. J. Org. Chem. 2012, 77, 7538.
  (b) Wu, X.; Chu, L.; Qing, F.-L. Angew. Chem. Int. Ed. 2013, 52, 2198.
  (c) Jiang, X.-Y.; Qing, F.-L. Angew. Chem. Int. Ed. 2013, 52, 14177.
  (d) Yu, W.; Xu, X.-H.; Qing, F.-L. Adv. Synth. Catal. 2015, 357, 2039.
  (e) Yang, B.; Xu, X.-H.; Qing, F.-L. Org. Lett. 2015, 17, 1906.
  (f) Lin, Q.-Y.; Xu, X.-H.; Zhang, K.; Qing, F.-L. Angew. Chem., Int. Ed. 2016, 55, 1479.
  (g) Yang, B.; Xu, X.-H.; Qing, F.-L. Chin. J. Chem. 2016, 34, 465.
  (h) Lin, Q.-Y.; Ran, Y.; Xu, X.-H.; Qing, F.-L. Org. Lett. 2016, 18, 2419.
  (i) Yu, W.; Xu, X.-H.; Qing, F.-L. Org. Lett. 2016, 18, 5130.
  (j) Yang, B.; Xu, X.-H.; Qing, F.-L. Org. Lett. 2016, 18, 5956.
  (k) Yang, B.; Yu, D.; Xu, X.-H.; Qing, F.-L. ACS Catal. 2018, 8, 2839.
  (l) Ouyang, Y.; Xu, X.-H.; Qing, F.-L. Angew. Chem., Int. Ed. 2018, 57, 6926.
11. [11]
  (a) Yin, F.; Wang, X.-S. Org. Lett. 2014, 16, 1128.
  (b) Guo, S.; Zhang, X.; Tang, P. Angew. Chem., Int. Ed. 2015, 54, 4065.
  (c) Wu, H.; Xiao, Z.; Wu, J.; Guo, Y.; Xiao, J.-C.; Liu, C.; Chen, Q.-Y. Angew. Chem., Int. Ed. 2015, 54, 4070.
  (d) Qiu, Y.-F.; Zhu, X.-Y.; Li, Y.-X.; He, Y.-T.; Yang, F.; Wang, J.; Hua, H.-L.; Zheng, L.; Wang, L.-C.; Liu, X.-Y.; Liang, Y.-M. Org. Lett. 2015, 17, 3694.
  (e) Zeng, Y.-F.; Tan, D.-H.; Chen, Y.; Lv, W.-X.; Liu, X.-G.; Li, Q.; Wang, H. Org. Chem. Front. 2015, 2, 1511.
  (f) Li, C.; Zhang, K.; Xu, X.-H.; Qing, F.-L. Tetrahedron Lett. 2015, 56, 6273.
  (g) Pan, S.; Huang, Y.; Qing, F. L. Chem. Asian J. 2016, 11, 2854.
  (h) Huang, F.-Q.; Wang, Y.-W.; Sun, J.-G.; Xie, J.; Qi, L.-W.; Zhang, B. RSC Adv. 2016, 6, 52710.
  (i) Song, Y.-K.; Qian, P.-C.; Chen, F.; Deng, C.-L.; Zhang, X.-G. Tetrahedron 2016, 72, 7589.
  (j) Ji, M. S.; Wu, Z.; Yu, J. J.; Wan, X. B.; Zhu, C. Adv. Synth. Catal. 2017, 359, 1959.
  (k) He, B.; Xiao, Z.; Wu, H.; Guo, Y.; Chen, Q.-Y.; Liu, C. RSC Adv. 2017, 7, 880.
  (l) Liu, K.; Jin, Q.; Chen, S.; Liu, P. N. RSC Adv. 2017, 7, 1546.
  (m) Li, M.; Petersen, J. L.; Hoover, J. M. Org. Lett. 2017, 19, 638.
  (n) Cheng, Z.-F.; Tao, T.-T.; Feng, Y.-S.; Tang, W.-K.; Xu, J.; Dai, J.-J.; Xu, H.-J. J. Org. Chem. 2018, 83, 499.
12. [12]
  (a) Ye, Y.; Sanford, M. S. J. Am. Chem. Soc. 2012, 134, 9034.
  (b) Huang, L.; Zheng, S.-C.; Tan, B.; Liu, X.-Y. Chem.-Eur. J. 2015, 18, 6718.
  (c) Yu, L.-Z.; Wei, Y.; Shi, M. Chem. Commun. 2016, 52, 13163.
  (d) Cheng, C.; Liu, S.; Lu, D.; Zhu, G. Org. Lett. 2016, 18, 2852.
13. [13]
  (a) Wu, W.; Zhang, X.; Liang, F.; Cao, S. Org. Biomol. Chem. 2015, 13, 6992.
  (b) Zhang, J.; Yang, J.-D.; Zheng, H.; Xue, X.-S.; Mayr, H.; Cheng, J.-P. Angew. Chem. Int. Ed. 2018, 57, 12690.
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