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.
1. [1]
  Jing-Qi Tao , Shuai Liu , Tian-Yu Zhang , Hong Xin , Xu Yang , Xin-Hua Duan , Li-Na Guo . Photoinduced copper-catalyzed alkoxyl radical-triggered ring-expansion/aminocarbonylation cascade. Chinese Chemical Letters, 2024, 35(6): 109263-. doi: 10.1016/j.cclet.2023.109263
2. [2]
  Yu-Yu Tan , Lin-Heng He , Wei-Min He . Copper-mediated assembly of SO₂F group via radical fluorine-atom transfer strategy. Chinese Chemical Letters, 2024, 35(9): 109986-. doi: 10.1016/j.cclet.2024.109986
3. [3]
  Hongping Zhao , Weiming Yuan . Merging catalytic electron donor-acceptor complex and copper catalysis: Enantioselective radical carbocyanation of alkenes. Chinese Chemical Letters, 2025, 36(10): 110894-. doi: 10.1016/j.cclet.2025.110894
4. [4]
  Qi Li , Zi-Lu Wang , Yun-He Xu . Copper-catalyzed 1,4-silylcyanation of 1,3-enynes: A silyl radical-initiated approach for synthesis of difunctionalized allenes. Chinese Chemical Letters, 2025, 36(3): 109991-. doi: 10.1016/j.cclet.2024.109991
5. [5]
  Yu Peng , Yue Wang , Tian-Jiao Chen , Jing-Jing Chen , Jin-Ling Yang , Ting Gong , Ping Zhu . A fungal CYP from Beauveria bassiana with promiscuous steroid hydroxylation capabilities. Chinese Chemical Letters, 2024, 35(5): 108818-. doi: 10.1016/j.cclet.2023.108818
6. [6]
  Yun Zhou , Geqian Fang , Haiyan Wang , Wenjun Yu , Chun Zhu , Jin-Xia Liang , Jian Lin . Non-covalent interactions between adsorbed •OH species and UiO-66-NH2 for methane hydroxylation. Chinese Journal of Structural Chemistry, 2025, 44(8): 100629-100629. doi: 10.1016/j.cjsc.2025.100629
7. [7]
  Ruixiang Wang , Jiajie Hou , Jinze He , Junyao Huang , Li Zhao , Ravi Naidu , Dionissios Mantzavinos , Grigorios Beligiannis , Nikolaos Andritsos , Fei Shen , Yongjia Lei . Surface hydroxylation engineering of pyrene-based COFs to promote oxygen activation for visible-light-catalyzed degradation of antibiotics. Chinese Chemical Letters, 2026, 37(6): 112143-. doi: 10.1016/j.cclet.2025.112143
8. [8]
  Nianhua Luo , Jiayi Jiang , Muhammad Suleman , Zhaowen Liu , Shuping Huang , Wei Xiao , Jie Wu , Jiapian Huang . Advances in radical Smiles rearrangement. Chinese Chemical Letters, 2026, 37(2): 111556-. doi: 10.1016/j.cclet.2025.111556
9. [9]
  Zhengzhong Zhu , Shaojun Hu , Zhi Liu , Lipeng Zhou , Chongbin Tian , Qingfu Sun . A cationic radical lanthanide organic tetrahedron with remarkable coordination enhanced radical stability. Chinese Chemical Letters, 2025, 36(2): 109641-. doi: 10.1016/j.cclet.2024.109641
10. [10]
  Shaonan Tian , Yu Zhang , Qing Zeng , Junyu Zhong , Hui Liu , Lin Xu , Jun Yang . Core-shell gold-copper nanoparticles: Evolution of copper shells on gold cores at different gold/copper precursor ratios. Chinese Journal of Structural Chemistry, 2023, 42(11): 100160-100160. doi: 10.1016/j.cjsc.2023.100160
11. [11]
  Pan Zhou , Ting Zou , Hong-Jian Song , Yu-Xiu Liu , Qing-Min Wang . Advances in organoelectrochemical copper-catalyzed reactions. Chinese Chemical Letters, 2026, 37(1): 111673-. doi: 10.1016/j.cclet.2025.111673
12. [12]
  Yalan Deng , Yaqi Wu , Haipeng Xiao , Nuowen Ma , Huifang Miao , Liuxuan Cao , Wei Guo . Synergistic phenol degradation via electron beam irradiation and bimetallic catalysis: Coupling radical and non-radical pathways. Chinese Chemical Letters, 2026, 37(9): 111568-. doi: 10.1016/j.cclet.2025.111568
13. [13]
  Jindian Duan , Xiaojuan Ding , Pui Ying Choy , Binyan Xu , Luchao Li , Hong Qin , Zheng Fang , Fuk Yee Kwong , Kai Guo . Oxidative spirolactonisation for modular access of γ-spirolactones via a radical tandem annulation pathway. Chinese Chemical Letters, 2024, 35(10): 109565-. doi: 10.1016/j.cclet.2024.109565
14. [14]
  Xiao-Bo Liu , Ren-Ming Liu , Xiao-Di Bao , Hua-Jian Xu , Qi Zhang , Yu-Feng Liang . Nickel-catalyzed reductive formylation of aryl halides via formyl radical. Chinese Chemical Letters, 2024, 35(12): 109783-. doi: 10.1016/j.cclet.2024.109783
15. [15]
  Hong-Qiang Dong , Shang-Bo Yu , Shu-Meng Wang , Jia-Hao Zhao , Xu-Guan Bai , Shi-Xing Lei , Zhen-Nan Tian , Jia Tian , Kang-Da Zhang , Lu Wang , Zhan-Ting Li , Shigui Chen . Construction of radical halogen-bonded organic frameworks with enhanced magnetism and conductivity. Chinese Chemical Letters, 2025, 36(8): 110730-. doi: 10.1016/j.cclet.2024.110730
16. [16]
  Hui-Xian Jiang , Zhi-Tao Liu , Pei Xu , Xu Zhu . Synthetic application of oxalate salts for visible-light-induced radical transformations. Chinese Chemical Letters, 2025, 36(12): 111224-. doi: 10.1016/j.cclet.2025.111224
17. [17]
  Saima Perveen , Lulu Qin , Min Zhao , Zhengwei Ding , Yingying Wang , Zaicheng Nie , Pengfei Li . Recent development in radical cycloaddition reactions for the synthesis of carbo- and heterocycles. Chinese Chemical Letters, 2026, 37(1): 111886-. doi: 10.1016/j.cclet.2025.111886
18. [18]
  Fuyang Yue , Fei Yuan , Kun Li , Xun Luo , Hongjian Song , Yuxiu Liu , Qingmin Wang . Synthesis of antifungal gem–difluoroallylsilane compounds via radical transfer strategy. Chinese Chemical Letters, 2026, 37(7): 111940-. doi: 10.1016/j.cclet.2025.111940
19. [19]
  Guoliang Liu , Zhiqiang Liu , Anmin Zheng . Modulation of zeolite surface realizes dynamic copper species redispersion. Chinese Journal of Structural Chemistry, 2024, 43(6): 100308-100308. doi: 10.1016/j.cjsc.2024.100308
20. [20]
  Luyao Lu , Chen Zhu , Fei Li , Pu Wang , Xi Kang , Yong Pei , Manzhou Zhu . Ligand effects on geometric structures and catalytic activities of atomically precise copper nanoclusters. Chinese Journal of Structural Chemistry, 2024, 43(10): 100411-100411. doi: 10.1016/j.cjsc.2024.100411

Get Citation

PDF

XML

Metrics

PDF Downloads(10)
Abstract views(1854)
HTML views(256)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142