SIOC 中文
CJOG
Adv search

Chinese Journal of Organic Chemistry >

2020 , Vol. 40 >Issue 11: 3873 - 3880

DOI: https://doi.org/10.6023/cjoc202006071

Electrochemical Allylic Hydrodefluorination Reaction Using Gaseous Ammonia as Hydrogen Source

  • Sheng Jie ,
  • Wu Na ,
  • Liu Xu ,
  • Liu Feng ,
  • Liu Shuai ,
  • Ding Weijie ,
  • Liu Chang ,
  • Cheng Xu
Expand
  • a Institute of Chemical and Biomedical Science, Jiangsu Advanced Organic Material Laboratory, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023;
    b State Key Laboratory of Elemento-organic Chemistry, Nankai University, Tianjin 300071

Received date: 2020-06-29

  Revised date: 2020-07-23

  Online published: 2020-08-06

Supported by

Project supported by the National Natural Science Foundation of China (Nos. 22071105, 22031008), the QingLan Project of Jiangsu Education Department and the National Key Research and Development Program of China (No. 2019YFC0408303).

Fold

Abstract

gem-Difluoroalkenes have wide applications in the drug designs and act as the synthon of molecules containing fluoride. The current researches on the electrochemical syntheses of gem-difluoroalkenes are limited to the silylation of enolated trifluoromethyl ketones. Herein, by using graphite felt as electrodes, the electrochemical allylic hydrodefluorination of α-trifluoromethyl cinnamates is realized using gaseous ammonia as hydrogen source, giving gem-difluorostyrenes in moderate to good yields. The usage of ammonia and graphite felt cathode is important to inhibit the cathodic hydrogen evolution, keeping the electron transfer from cathode to substrate with high selectivity. The cyclic voltammetry (CV) and square wave voltammetry (SWV) analyses support a stepwise electron transfer process to achieve the C—H bond formation and C—F bond cleavage.

Key words： electrochemistry; ammonia; C-F bond activation; graphite felt electrode

Cite this article

Sheng Jie , Wu Na , Liu Xu , Liu Feng , Liu Shuai , Ding Weijie , Liu Chang , Cheng Xu . Electrochemical Allylic Hydrodefluorination Reaction Using Gaseous Ammonia as Hydrogen Source[J]. Chinese Journal of Organic Chemistry, 2020 , 40(11) : 3873 -3880 . DOI: 10.6023/cjoc202006071

References

[1] (a) McDonald, I. A.; Lacoste, J. M.; Bey, P.; Palfreyman, M. G.; Zreika, M. J. Med. Chem. 1985, 28, 186.
(b) Sayre, L. M. WO2007005737A2. 2007.
[2] Okada, H.; Morita, M.; Ueda, T.; Takeo, H.; Kominami, H.; Kiriyama, K.; Nakamoto, K.; Yoshida, Y. WO2004052872A1, 2004.
[3] Koley, S.; Altman, R. A. Isr. J. Chem. 2020, 60, 313.
[4] (a) Gao, B.; Zhao, Y.; Ni, C.; Hu, J. Org. Lett. 2014, 16, 102.
(b) Gao, B.; Zhao, Y.; Hu, J. Angew. Chem., Int. Ed. 2015, 54, 638.
[5] (a) Tian, P.; Feng, C.; Loh, T.-P. Nat. Commun. 2015, 6, 7472.
(b) Tian, P.; Wang, C.-Q.; Cai, S.-H.; Song, S.; Ye, L.; Feng, C.; Loh, T.-P. J. Am. Chem. Soc. 2016, 138, 15869.
(c) Cai, S.-H.; Ye, L.; Wang, D.-X.; Wang, Y.-Q.; Lai, L.-J.; Zhu, C.; Feng, C.; Loh, T.-P. Chem. Commun. 2017, 53, 8731.
(d) Tang, H.-J.; Lin, L.-Z.; Feng, C.; Loh, T.-P. Angew. Chem., Int. Ed. 2017, 56, 9872.
(e) Zhu, C.; Song, S.; Zhou, L.; Wang, D.-X.; Feng, C.; Loh, T.-P. Chem. Commun. 2017, 53, 9482.
(f) Tang, H.-J.; Zhang, Y.-F.; Jiang, Y.-W.; Feng, C. Org. Lett. 2018, 20, 5190.
(g) Zhou, L.; Zhu, C.; Loh, T.-P.; Feng, C. Chem. Commun. 2018, 54, 5618.
(h) Liu, H.; Ge, L.; Wang, D.-X.; Chen, N.; Feng, C. Angew. Chem., Int. Ed. 2019, 58, 3918.
(i) Zhou, L.; Zhu, C.; Bi, P.; Feng, C. Chem. Sci. 2019, 10, 1144.
(j) Zhu, C.; Zhang, Y.-F.; Liu, Z.-Y.; Zhou, L.; Liu, H.; Feng, C. Chem. Sci. 2019, 10, 6721.
(k) Cao, Z.-C.; Liu, J.-C.; Chu, Y.-Q.; Zhao, F.-M.; Zhu, Y.-H.; She, Y.-B. Chin. J. Org. Chem. 2019, 39, 2499(in Chinese). (曹志成, 刘建超, 褚有群, 赵峰鸣, 朱英红, 佘远斌, 有机化学2019, 39, 2499.)
(l) Du, H.-W.; Sun, J.; Gao, Q.-S.; Wang, J.-Y.; Wang, H.; Xu, Z.; Zhou, M.-D. Org. Lett. 2020, 22, 1542.
[6] Zubkov, M. O.; Kosobokov, M. D.; Levin, V. V.; Kokorekin, V. A.; Korlyukov, A. A.; Hu, J.; Dilman, A. D. Chem. Sci. 2020, 11, 737.
[7] Liu, C.; Zhu, C.; Cai, Y.; Yang, Z.; Zeng, H.; Chen, F.; Jiang, H. Chem.-Eur. J. 2020, 26, 1953.
[8] Chelucci, G. Chem. Rev. 2012, 112, 1344.
[9] Nihei, T.; Iwai, N.; Matsuda, T.; Kitazume, T. J. Org. Chem. 2005, 70, 5912.
[10] Cao, C.-R.; Ou, S.; Jiang, M.; Liu, J.-T. Tetrahedron Lett. 2017, 58, 482.
[11] Wang, S.; Cheng, B.-Y.; Sršen, M.; König, B. J. Am. Chem. Soc. 2020, 142, 7524.
[12] Yu, J.; Lin, J.-H.; Xiao, J.-C. Chin. J. Org. Chem. 2019, 39, 265(in Chinese). (于蛟, 林锦鸿, 肖吉昌, 有机化学, 2019, 39, 265.)
[13] Guo, S.; Yang, P.; Zhou, J. Chem. Commun. 2015, 51, 12115.
[14] (a) Chen, J.; Lv, S.; Tian, S. ChemSusChem 2019, 12, 115.
(b) Gandeepan, P.; Kaplaneris, N.; Santoro, S.; Vaccaro, L.; Ackermann, L. ACS Sustainable Chem. Eng. 2019, 7, 8023.
(c) Mei, H.; Yin, Z.; Liu, J.; Sun, H.; Han, J. Chin. J. Chem. 2019, 37, 292.
(d) Meyer, T. H.; Finger, L. H.; Gandeepan, P.; Ackermann, L. Trends Chem. 2019, 1, 63.
(e) Qiu, Y.; Struwe, J.; Ackermann, L. Synlett 2019, 30, 1164.
(f) Song, C.; Liu, K.; Dong, X.; Chiang, C.-W.; Lei, A. Synlett 2019, 30, 1149.
(g) Wang, H.; Gao, X.; Lv, Z.; Abdelilah, T.; Lei, A. Chem. Rev. 2019, 119, 6769.
(h) Xiong, P.; Xu, H.-C. Acc. Chem. Res. 2019, 52, 3339.
(i) Ye, Z.; Zhang, F. Chin. J. Chem. 2019, 37, 513.
(j) Yuan, Y.; Lei, A. Acc. Chem. Res. 2019, 52, 3309.
(k) Zhang, H.-Y.; Tang, R.-P.; Shi, X.-L.; Jie, L.; Wu, J.-W. Chin. J. Org. Chem. 2019, 39, 1837(in Chinese). (张怀远, 唐蓉萍, 石星丽, 颉林, 伍家卫, 有机化学, 2019, 39, 1837.)
(l) Ackermann, L. Acc. Chem. Res. 2020, 53, 84.
(m) Jiao, K.-J.; Xing, Y.-K.; Yang, Q.-L.; Qiu, H.; Mei, T.-S. Acc. Chem. Res. 2020, 53, 300.
(n) Li, M.; Hong, J.; Xiao, W.; Yang, Y.; Qiu, D.; Mo, F. ChemSusChem 2020, 13, 1661.
(o) Rockl, J. L.; Pollok, D.; Franke, R.; Waldvogel, S. R. Acc. Chem. Res. 2020, 53, 45.
(p) Wang, P.; Gao, X. L.; Huang, P. F.; Lei, A. W. ChemCatChem 2020, 12, 27.
(q) Wang, X.-Y.; Xu, X.-T.; Wang, Z.-H.; Fang, P.; Mei. T.-S. Chin. J. Org. Chem. 2020, 40, 3738(in Chinese). (王向阳, 徐学涛, 王振华, 方萍, 梅天胜, 有机化学, 2020, 40, 3738.)
[15] Peters, D. G.; McGuire, C. M.; Pasciak, E. M.; Peverly, A. A.; Strawsine, L. M.; Wagoner, E. R.; Barnes, J. T. Rev. Soc. Quim. Mex. 2017, 58, 287.
[16] Huang, H.; Lambert, T. H. Angew. Chem., Int. Ed. 2020, 59, 658.
[17] (a) Uneyama, K.; Kato, T. Tetrahedron Lett. 1998, 39, 587.
(b) Uneyama, K.; Maeda, K.; Kato, T.; Katagiri, T. Tetrahedron Lett. 1998, 39, 3741.
(c) Uneyama, K.; Mizutani, G. Chem. Commun. 1999, 613.
(d) Uneyama, K.; Mizutani, G.; Maeda, K.; Kato, T. J. Org. Chem. 1999, 64, 6717.
[18] (a) Liu, X.; Liu, R.; Qiu, J.; Cheng, X.; Li, G. Angew. Chem., Int. Ed., 2020, 59, 13962.
(b) Li, J.; He, L.; Liu, X.; Cheng, X.; Li, G. Angew. Chem., Int. Ed. 2019, 58, 1759.
Options
Outlines

/

〈 〉