Citation: Gou Baoquan, Yang Chao, Zhang Lei, Xia Wujiong. Visible-Light Induced Trifluoromethylation of Internal Olefinic C-H Bonds through Photoredox Catalysis[J]. Acta Chimica Sinica, ;2017, 75(1): 66-69. doi: 10.6023/A16070341 shu

Visible-Light Induced Trifluoromethylation of Internal Olefinic C-H Bonds through Photoredox Catalysis

School of Chemistry and Chemical Engineering, State Key Lab of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150080

Corresponding author: Yang Chao, xyyang@hit.edu.cn Xia Wujiong, xiawj@hit.edu.cn
Received Date: 15 July 2016

Fund Project: State Key Laboratory of Urban Water Resource and Environment 2015DX01National Natural Science Foundation of China 21472030National Natural Science Foundation of China 21372055National Natural Science Foundation of China 21272047and the Fundamental Research Funds for the Central Universities HIT.BRETIV.201310

Figures(4)

An approach for direct trifluoromethylation of internal olefins of α-oxoketene dithioacetals has been achieved by using Ru (bpy)₃Cl₂ as photocatalyst and Togni's reagent as trifluoromethylating agent under irradiation with visible light. Under a nitrogen atmosphere, a mixture of α-oxoketene dithioacetal (0.1 mmol), Togni's reagent (0.15 mmol), Ru (bpy)₃Cl₂ (0.005 mmol), and Na₂CO₃ (0.3 mmol) in DMSO (1 mL) was stirred at room temperature for 72 h under 5 W Blue LEDS, which led to the trifluoromethylated products in 40%~90% yield. This protocol provides an efficient and easy access to prepare trifluoromethylated dithioalkyl α-oxoketene acetals under mild conditions, and is highlighted by its operational simplicity and avoiding using toxic reagent. Furthermore, the gram-scale reaction of 1a suggested the potential application of this protocol in organic synthesis.
- visible light,
- olefin,
- trifluoromethylation,
- photocatalyst,
- operational simplicity
1. [1]
  Kirsch, P. Modern Fluoro-Organic Chemistry, Wiley-VCH, Weinheim, 2004.
2. [2]
  (a) Müller, K.; Faeh, C.; Diederich, F. Science 2007, 317, 1881. (b) O'Hagan, D. Chem. Soc. Rev. 2008, 37, 308. (c) Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, V. Chem. Soc. Rev. 2008, 37, 320. (d) Furuya, T.; Kamlet, A. S.; Ritter, T. Nature 2011, 473, 470.
3. [3]
  Liu, Y. X.; Shimizu, M.; Hiyama, T. Angew. Chem., Int. Ed. 2004, 43, 879. doi: 10.1002/(ISSN)1521-3773
4. [4]
  (a) Liang, T.; Neumann, C. N.; Ritter, T. Angew. Chem., Int. Ed. 2013, 52, 8214.(b) Charpentier, J.; Früh, N.; Togni, A. Chem. Rev. 2015, 115, 650. (c) Alonso, C.; Marigorta, E. M.; Rubiales, G.; Palacios, F. Chem. Rev. 2015, 115, 1847. (d) Zeng, T.; Xuan, J.; Chen, J.; Lu, L.; Xiao, W. Imag. Sci. Photochem. 2014, 32, 415. (e) Peng, R.; Yang, B.; Chen, Z.; Xu, L.; Wang, S. Chin. J. Org. Chem. 2014, 34, 980. (彭蕊, 杨彬淼, 陈志敏, 徐力, 王少华, 有机化学, 2014, 34, 980.) (f) Wang, G.; He, X.; Dai, J.; Xu, H. Chin. J. Org. Chem. 2014, 34, 837. (王光祖, 赫侠平, 戴建军, 许华建, 有机化学, 2014, 34, 837.) (g) Zhang, Q.; Jin, C.; Zhang, Y. Chin. J. Org. Chem. 2014, 34, 662. (张霁, 金传飞, 张英俊, 有机化学, 2014, 34, 662.) (h) He, Z.; Huang, Y.; Francis, V. Acta Chim. Sinica 2013, 71, 700. (何展荣, 黄毅勇, Francis, V.化学学报, 2013, 71, 700.)
5. [5]
  Sanhueza, I. A.; Bonney, K. J.; Nielsen, M. C.; Schoenebeck, F. J. Org. Chem. 2013, 78, 7749. doi: 10.1021/jo401099e
6. [6]
  Zhang, Y. Q.; Liu, J. D.; Xu, H. Org. Biomol. Chem. 2013, 11, 6242. doi: 10.1039/c3ob41283k
7. [7]
  For selected recent reports on addition of CF₃ reagents to alkenes, see: (a) Zhu, R.; Buchwald, S. L. J. Am. Chem. Soc. 2012, 134, 12462. (b) Egami, H.; Shimizu, R.; Kawamura, S.; Sodeoka, M. Angew. Chem., Int. Ed. 2013, 52, 4000. (c) Deb, A.; Manna, S.; Modak, A.; Patra, T.; Maity, S.; Maiti, D. Angew. Chem. Int. Ed. 2013, 52, 9747. (d) Wang, X.; Ye, Y. X.; Zhang, S. N.; Feng, J. J.; Xu, Y.; Zhang, Y.; Wang, J. B. J. Am. Chem. Soc. 2011, 133, 16410.
8. [8]
  Mao, Z. F.; Huang, F.; Yu, H. F.; Chen, J. P.; Yu. Z. K.; Xu, Z. Q. Chem. Eur. J. 2014, 20, 3439. doi: 10.1002/chem.v20.12
9. [9]
  For selected recent reports on the trifluoromethylation of aromatics, see: (a) Ye, Y. D.; Sanford, M. S. J. Am. Chem. Soc. 2012, 134, 9034. (b) Zeng, Y. W.; Zhang, L. J.; Zhao, Y. C.; Ni, C. F.; Zhao, J. W.; Hu, J. B. J. Am. Chem. Soc. 2013, 135, 2955. (c) Wang, X.; Xu, Y.; Mo, F. Y.; Ji, G.; Qiu, D.; Feng, J. J.; Ye, Y. X.; Zhang, S. N.; Zhang, Y.; Wang, J. B. J. Am. Chem. Soc. 2013, 135, 10330.(d) Hafner, A.; Bräse, S. Angew. Chem., Int. Ed. 2012, 51, 3713.
10. [10]
  For selected recent examples, see: (a) Hu, M. Y.; Ni, C. F.; Hu, J. B. J. Am. Chem. Soc. 2012, 134, 15257. (b) Novk, P.; Lishchynskyi, A.; Grushin, V. V. J. Am. Chem. Soc. 2012, 134, 16167. (c) Shimizu, R.; Egami, H.; Hamashima, Y.; Sodeoka, M. Angew. Chem., Int. Ed. 2012, 51, 4577.(d) Niedermann, K.; Früh, N.; Senn, R.; Czarniecki, B.; Verel, R.; Togni, A. Angew. Chem., Int. Ed. 2012, 51, 6511. (e) Li, Z.; Gevorgyan, V. Angew. Chem., Int. Ed. 2012, 51, 1225.
11. [11]
  For Selected recent reports, see: (a) He, Z.; Luo, T.; Hu, M. Y.; Cao, Y. J.; Hu, J. B. Angew. Chem., Int. Ed. 2012, 51, 3944. (b) Li, Y.; Wu, L. P.; Neumann, H.; Beller, M. Chem. Commun. 2013, 49, 2628.
12. [12]
  Janson, P. G.; Ghoneim, I.; Ilchenko, N. O.; Szab, K. J. Org. Lett. 2012, 14, 2882. doi: 10.1021/ol3011419
13. [13]
  Omote, M.; Tanaka, M.; Ikeda, A.; Nomura, S.; Tarui, A.; Sato, K.; Ando, A. Org. Lett. 2012, 14, 2286. doi: 10.1021/ol300670n
14. [14]
  For selected recent examples of transition-metal-catalyzed (hetero) arene C-H Trifluoromethylation, see: (a) Zhang, X.-G.; Dai, H.-X.; Wasa, M.; Yu, J.-Q. J. Am. Chem. Soc. 2012, 134, 11948. (b) Seo, S.; Taylor, J. B.; Greaney, M. F. Chem. Commun. 2013, 49, 6385. (c) Chu, L. L.; Qing, F.-L. J. Am. Chem. Soc. 2012, 134, 1298. (d) Mejia, E.; Togni, A. ACS Catal. 2012, 2, 521. (e) Ji, Y. L.; Brueckl, T.; Baxter, R. D.; Fujiwara, Y.; Seiple, I. B.; Su, S.; Blackmond, D. G.; Baran, P. S. Proc. Natl. Acad. Sci. USA 2011, 108, 14411. (f) Ye, Y. D.; Lee, S. H.; Sanford, M. S. Org. Lett. 2011, 13, 5464. (g) Mu, X.; Chen, S. J.; Zhen, X. L.; Liu, G. S. Chem. Eur. J. 2011, 17, 6039. (h) Wang, X. S.; Truesdale, L.; Yu, J.-Q. J. Am. Chem. Soc. 2010, 132, 3648.
15. [15]
  (a) Yang, Y. D.; Iwamoto, K.; Tokunaga, E.; Shibata, N. Chem. Commun. 2013, 49, 5510. (b) Wu, X. Y.; Chu, L. L.; Qing, F.-L. Tetrahedron Lett. 2013, 54, 249.
16. [16]
  (a) Ilchenko, N. O.; Janson, P. G.; Szab, K. J. Chem. Commun. 2013, 49, 6614. (b) Wang, X.; Ye, Y. X.; Ji, G. J.; Xu, Y.; Zhang, S. N.; Feng, J. J.; Zhang, Y.; Wang, J. B. Org. Lett. 2013, 15, 3730. (c) Uraguchi, D.; Yamamoto, K.; Ohtsuka, Y.; Tokuhisa, K.; Yamakawa, T. Appl. Catal. A 2008, 342, 137. (d) Feng, C.; Loh, T.-P. Chem. Sci. 2012, 3, 3458. (e) Feng, C.; Loh, T.-P. Angew. Chem., Int. Ed. 2013, 52, 12414. (f) Besset, T.; Cahard, D.; Pannecoucke, X. J. Org. Chem. 2014, 79, 413. (g) Jiang, H.; Huang, C. M.; Guo, J. J.; Zeng, C. Q.; Zhang, Y.; Yu, S. Y. Chem. Eur. J. 2012, 18, 15158. (h) Iqbal, N.; Choi, S.; Kim, E.; Cho, E. J. J. Org. Chem. 2012, 77, 11383. (i) Yasu, Y.; Koike, T.; Akita, M. Angew. Chem., Int. Ed. 2012, 51, 9567.
17. [17]
  (a) Yu, H. F.; Yu, Z. K. Angew. Chem., Int. Ed. 2009, 48, 2929. (b) Yu, H. F.; Jin, W. W.; Sun, C. L.; Chen, J. P.; Du, W. M.; He, S. B.; Yu, Z. K. Angew. Chem., Int. Ed. 2010, 49, 5792. (c) Pan, L.; Bi, X. H.; Liu, Q. Chem. Soc. Rev. 2013, 42, 1251.
18. [18]
  Wang, L. D.; He, W.; Yu, Z. K. Chem. Soc. Rev. 2013, 42, 599. doi: 10.1039/C2CS35323G
19. [19]
  Junjappa, H.; Ila, H.; Asokan, C. V. Tetrahedron 1990, 46, 5423. doi: 10.1016/S0040-4020(01)87748-6
20. [20]
  Selected recent reports:(a) Fu, Z. Q.; Wang, M.; Ma, Y. H.; Liu, Q.; Liu, J. J. Org. Chem. 2008, 73, 7625. (b) Misra, N. C.; Panda, K.; Ila, H.; Junjappa, H. J. Org. Chem. 2007, 72, 1246. (c) Rao, H. S. P.; Sivakumar, S. J. Org. Chem. 2006, 71, 8715.
21. [21]
  Selected recent reports:(a) Hu, J. L.; Zhang, Q.; Yuan, H. J.; Liu, Q. J. Org. Chem. 2008, 73, 2442. (b) Bi, X. H.; Dong, D. W.; Liu, Q.; Pan, W.; Zhao, L.; Li, B. J. Am. Chem. Soc. 2005, 127, 4578. (c) Sundaram, G. S. M.; Venkatesh, C.; Kumar, U. K. S.; Ila, H.; Junjappa, H. J. Org. Chem. 2004, 69, 5760.
22. [22]
  Selected recent reports:(a) Yu, H. F.; Dong, D. W.; Ouyang, Y.; Wang, Y.; Liu, Q. Synlett 2007, 151. (b) Dong, D. W.; Ouyang, Y.; Yu, H. F.; Liu, Q.; Liu, J.; Wang, M.; Zhu, J. J. Org. Chem. 2005, 70, 4535.
23. [23]
  Xu, C.; Liu, J. X.; Ming, W. B.; Liu, Y. J.; Liu, J.; Wang, M.; Liu, Q. Chem. Eur. J. 2013, 19, 9104. doi: 10.1002/chem.v19.28
1. [1]
  Bing LIU , Huang ZHANG , Hongliang HAN , Changwen HU , Yinglei ZHANG . Visible light degradation of methylene blue from water by triangle Au@TiO₂ mesoporous catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 941-952. doi: 10.11862/CJIC.20230398
2. [2]
  Qiang ZHAO , Zhinan GUO , Shuying LI , Junli WANG , Zuopeng LI , Zhifang JIA , Kewei WANG , Yong GUO . Cu₂O/Bi₂MoO₆ Z-type heterojunction: Construction and photocatalytic degradation properties. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 885-894. doi: 10.11862/CJIC.20230435
3. [3]
  Tingting Liu , Pengfei Sun , Wei Zhao , Yingshuang Li , Lujun Cheng , Jiahai Fan , Xiaohui Bi , Xiaoping Dong . Magnesium doping to improve the light to heat conversion of OMS-2 for formaldehyde oxidation under visible light irradiation. Chinese Chemical Letters, 2024, 35(4): 108813-. doi: 10.1016/j.cclet.2023.108813
4. [4]
  Ziruo Zhou , Wenyu Guo , Tingyu Yang , Dandan Zheng , Yuanxing Fang , Xiahui Lin , Yidong Hou , Guigang Zhang , Sibo Wang . Defect and nanostructure engineering of polymeric carbon nitride for visible-light-driven CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(3): 100245-100245. doi: 10.1016/j.cjsc.2024.100245
5. [5]
  Tian-Yu Gao , Xiao-Yan Mo , Shu-Rong Zhang , Yuan-Xu Jiang , Shu-Ping Luo , Jian-Heng Ye , Da-Gang Yu . Visible-light photoredox-catalyzed carboxylation of aryl epoxides with CO₂. Chinese Chemical Letters, 2024, 35(7): 109364-. doi: 10.1016/j.cclet.2023.109364
6. [6]
  Lang Gao , Cen Zhou , Rui Wang , Feng Lan , Bohang An , Xiaozhou Huang , Xiao Zhang . Unveiling inverse vulcanized polymers as metal-free, visible-light-driven photocatalysts for cross-coupling reactions. Chinese Chemical Letters, 2024, 35(4): 108832-. doi: 10.1016/j.cclet.2023.108832
7. [7]
  Jing Wang , Zenghui Li , Xiaoyang Liu , Bochao Su , Honghong Gong , Chao Feng , Guoping Li , Gang He , Bin Rao . Fine-tuning redox ability of arylene-bridged bis(benzimidazolium) for electrochromism and visible-light photocatalysis. Chinese Chemical Letters, 2024, 35(9): 109473-. doi: 10.1016/j.cclet.2023.109473
8. [8]
  Kun Tang , Yu-Wu Zhong . Water reduction by an organic single-chromophore photocatalyst. Chinese Journal of Structural Chemistry, 2024, 43(8): 100376-100376. doi: 10.1016/j.cjsc.2024.100376
9. [9]
  Xinyu You , Xin Zhang , Shican Jiang , Yiru Ye , Lin Gu , Hexun Zhou , Pandong Ma , Jamal Ftouni , Abhishek Dutta Chowdhury . Efficacy of Ca/ZSM-5 zeolites derived from precipitated calcium carbonate in the methanol-to-olefin process. Chinese Journal of Structural Chemistry, 2024, 43(4): 100265-100265. doi: 10.1016/j.cjsc.2024.100265
10. [10]
  Yi Liu , Zhe-Hao Wang , Guan-Hua Xue , Lin Chen , Li-Hua Yuan , Yi-Wen Li , Da-Gang Yu , Jian-Heng Ye . Photocatalytic dicarboxylation of strained C–C bonds with CO₂ via consecutive visible-light-induced electron transfer. Chinese Chemical Letters, 2024, 35(6): 109138-. doi: 10.1016/j.cclet.2023.109138
11. [11]
  Yiyue Ding , Qiuxiang Zhang , Lei Zhang , Qilu Yao , Gang Feng , Zhang-Hui Lu . Exceptional activity of amino-modified rGO-immobilized PdAu nanoclusters for visible light-promoted dehydrogenation of formic acid. Chinese Chemical Letters, 2024, 35(7): 109593-. doi: 10.1016/j.cclet.2024.109593
12. [12]
  Qiongqiong Wan , Yanan Xiao , Guifang Feng , Xin Dong , Wenjing Nie , Ming Gao , Qingtao Meng , Suming Chen . Visible-light-activated aziridination reaction enables simultaneous resolving of C=C bond location and the sn-position isomers in lipids. Chinese Chemical Letters, 2024, 35(4): 108775-. doi: 10.1016/j.cclet.2023.108775
13. [13]
  Haojie Song , Laiyu Luo , Siyu Wang , Guo Zhang , Baojiang Jiang . Advances in poly(heptazine imide)/poly(triazine imide) photocatalyst. Chinese Chemical Letters, 2024, 35(10): 109347-. doi: 10.1016/j.cclet.2023.109347
14. [14]
  Ping Lu , Baoyin Du , Ke Liu , Ze Luo , Abiduweili Sikandaier , Lipeng Diao , Jin Sun , Luhua Jiang , Yukun Zhu . Heterostructured In2O3/In2S3 hollow fibers enable efficient visible-light driven photocatalytic hydrogen production and 5-hydroxymethylfurfural oxidation. Chinese Journal of Structural Chemistry, 2024, 43(8): 100361-100361. doi: 10.1016/j.cjsc.2024.100361
15. [15]
  Bicheng Zhu , Jingsan Xu . S-scheme heterojunction photocatalyst for H2 evolution coupled with organic oxidation. Chinese Journal of Structural Chemistry, 2024, 43(8): 100327-100327. doi: 10.1016/j.cjsc.2024.100327
16. [16]
  Zongyi Huang , Cheng Guo , Quanxing Zheng , Hongliang Lu , Pengfei Ma , Zhengzhong Fang , Pengfei Sun , Xiaodong Yi , Zhou Chen . Efficient photocatalytic biomass-alcohol conversion with simultaneous hydrogen evolution over ultrathin 2D NiS/Ni-CdS photocatalyst. Chinese Chemical Letters, 2024, 35(7): 109580-. doi: 10.1016/j.cclet.2024.109580
17. [17]
  Yuhao Ma , Yufei Zhou , Mingchuan Yu , Cheng Fang , Shaoxia Yang , Junfeng Niu . Covalently bonded ternary photocatalyst comprising MoSe₂/black phosphorus nanosheet/graphitic carbon nitride for efficient moxifloxacin degradation. Chinese Chemical Letters, 2024, 35(9): 109453-. doi: 10.1016/j.cclet.2023.109453
18. [18]
  Chaoqun Ma , Yuebo Wang , Ning Han , Rongzhen Zhang , Hui Liu , Xiaofeng Sun , Lingbao Xing . Carbon dot-based artificial light-harvesting systems with sequential energy transfer and white light emission for photocatalysis. Chinese Chemical Letters, 2024, 35(4): 108632-. doi: 10.1016/j.cclet.2023.108632
19. [19]
  Dong-Sheng Deng , Su-Qin Tang , Yong-Tu Yuan , Ding-Xiong Xie , Zhi-Yuan Zhu , Yue-Mei Huang , Yun-Lin Liu . C-F insertion reaction sheds new light on the construction of fluorinated compounds. Chinese Chemical Letters, 2024, 35(8): 109417-. doi: 10.1016/j.cclet.2023.109417
20. [20]
  Rui Wang , He Qi , Haijiao Zheng , Qiong Jia . Light/pH dual-responsive magnetic metal-organic frameworks composites for phosphorylated peptide enrichment. Chinese Chemical Letters, 2024, 35(7): 109215-. doi: 10.1016/j.cclet.2023.109215

Get Citation

PDF

XML

Metrics

PDF Downloads(8)
Abstract views(666)
HTML views(111)

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