Citation: Feng Enqi, Hou Zhongwei, Xu Haichao. Electrochemical Synthesis of Tetrasubstituted Hydrazines by Dehydrogenative N-N Bond Formation[J]. Chinese Journal of Organic Chemistry, ;2019, 39(5): 1424-1428. doi: 10.6023/cjoc201812007 shu

Electrochemical Synthesis of Tetrasubstituted Hydrazines by Dehydrogenative N-N Bond Formation

College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005

Corresponding author: Xu Haichao, haichao.xu@xmu.edu.cn
Received Date: 4 December 2018
Revised Date: 27 December 2018
Available Online: 18 May 2019
Fund Project: the National Foundation for Fostering Talents in Basic Science J131002the National Natural Science Foundation of China 21672178Project supported by the National Natural Science Foundation of China (No. 21672178) and the National Foundation for Fostering Talents in Basic Science (No. J1310024)

Figures(2)

An electrochemical synthesis of tetrasubstituted hydrazines through dehydrogenative dimerization of secondary amines has been developed. The reactions are conducted in a simple undivided cell with constant current. The use of electricity to promote the reactions obviates the need for transition metal catalysts and oxidizing reagents, providing an efficient and sustainable access to tetrasubstituted hydrazines with diverse electronic properties.
- organic electrosynthesis,
- anodic oxidation,
- dehydrogenative coupling,
- tetrasubstituted hydrazines
1. [1]
  (a) Blair, L. M.; Sperry, J. J. Nat. Prod. 2013, 76, 794.
  (b) Zhang, Q.; Mándi, A.; Li, S.; Chen, Y.; Zhang, W.; Tian, X.; Zhang, H.; Li, H.; Zhang, W.; Zhang, S.; Ju, J.; Kurtán, T.; Zhang, C. Eur. J. Org. Chem. 2012, 5256.
  (c) Shoeb, M.; Celik, S.; Jaspars, M.; Kumarasamy, Y.; MacManus, S. M.; Nahar, L.; Thoo-Lin, P. K.; Sarker, S. D. Tetrahedron 2005, 61, 9001.
  (d) Higashibayashi, S.; Pandit, P.; Haruki, R.; Adachi, S.-i.; Kumai, R. Angew. Chem., Int. Ed. 2016, 55, 10830.
2. [2]
  Hou, Z. W.; Mao, Z. Y.; Melcamu, Y. Y.; Lu, X.; Xu, H.-C. Angew. Chem., Int. Ed. 2018, 57, 1636. doi: 10.1002/anie.v57.6
3. [3]
  (a) Reddy, C. B. R.; Reddy, S. R.; Naidu, S. Catal. Commun. 2014, 56, 50.
  (b) Yan, X.-M.; Chen, Z.-M.; Yang, F.; Huang, Z.-Z. Synlett 2011, 2011, 569.
  (c) Ryan, M. C.; Martinelli, J. R.; Stahl, S. S. J. Am. Chem. Soc. 2018, 140, 9074.
  (d) Fritsche, R. F.; Theumer, G.; Kataeva, O.; Knolker, H. J. Angew. Chem., Int. Ed. 2017, 56, 549.
  (e) Zhu, Y.; Shi, Y. Org. Lett. 2013, 15, 1942.
4. [4]
  (a) Yan, M.; Kawamata, Y.; Baran, P. S. Chem. Rev. 2017, 117, 13230.
  (b) Tang, S.; Liu, Y.; Lei, A. Chem 2018, 4, 27.
  (c) Jiang, Y.; Xu, K.; Zeng, C. Chem. Rev. 2018, 118, 4485.
  (d) Yang, Q. L.; Fang, P.; Mei, T. S. Chin. J. Chem. 2018, 36, 338.
  (e) Wiebe, A.; Gieshoff, T.; Mö hle, S.; Rodrigo, E.; Zirbes, M.; Waldvogel Siegfried, R.
  Angew. Chem., Int. Ed. 2018, 57, 5594.
  (f) Moeller, K. D. Chem. Rev. 2018, 118, 4817.
  (g) Yoshida, J.; Kataoka, K.; Horcajada, R.; Nagaki, A. Chem. Rev. 2008, 108, 2265.
  (h) Francke, R.; Little, R. D. Chem. Soc. Rev. 2014, 43, 2492.
5. [5]
  (a) Hayashi, R.; Shimizu, A.; Yoshida, J. J. Am. Chem. Soc. 2016, 138, 8400.
  (b) Horn, E. J.; Rosen, B. R.; Chen, Y.; Tang, J.; Chen, K.; Eastgate, M. D.; Baran, P. S. Nature 2016, 533, 77.
  (c) Wang, P.; Tang, S.; Huang, P.; Lei, A. Angew. Chem., Int. Ed. 2017, 56, 3009.
  (d) Fu, N.; Li, L.; Yang, Q.; Luo, S. Org. Lett. 2017, 19, 2122.
  (e) Feng, R.; Smith, J. A.; Moeller, K. D. Acc. Chem. Res. 2017, 50, 2346.
  (f) Yang, Q. L.; Li, Y. Q.; Ma, C.; Fang, P.; Zhang, X. J.; Mei, T. S. J. Am. Chem. Soc. 2017, 139, 3293.
  (g) Zhang, S.; Li, L.; Xue, M.; Zhang, R.; Xu, K.; Zeng, C. Org. Lett. 2018, 20, 3443.
  (h) Fu, N.; Sauer, G. S.; Saha, A.; Loo, A.; Lin, S. Science 2017, 357, 575.
  (i) Li, J.; Huang, W.; Chen, J.; He, L.; Cheng, X.; Li, G. Angew. Chem., Int. Ed. 2018, 57, 5695.
  (j) Yuan, Y.; Cao, Y.; Qiao, J.; Lin, Y.; Jiang, X.; Weng, Y.; Tang, S.; Lei, A. Chin. J. Chem. 2019, 37, 49.
  (k) Ye, Z. H.; Ding, M. R.; Wu, Y. Q.; Li, Y.; Hua, W. K.; Zhang, F. Z. Green Chem. 2018, 20, 1732.
  (l) Qian, P.; Su, J.-H.; Wang, Y.; Bi, M.; Zha, Z.; Wang, Z. J. Org. Chem. 2017, 82, 6434.
  (m) Lin, D. Z.; Huang, J. M. Org. Lett. 2018, 20, 2112.
  (n) Zhang, L.; Zhang, Z. X.; Hong, J. T.; Yu, J.; Zhang, J. N.; Mo, F. Y. J. Org. Chem. 2018, 83, 3200.
6. [6]
  Rosen, B. R.; Werner, E. W.; O'Brien, A. G.; Baran, P. S. J. Am. Chem. Soc. 2014, 136, 5571. doi: 10.1021/ja5013323
7. [7]
  (a) Zhu, L.; Xiong, P.; Mao, Z. Y.; Wang, Y. H.; Yan, X.; Lu, X.; Xu, H.-C. Angew. Chem., Int. Ed. 2016, 55, 2226.
  (b) Xiong, P.; Xu, H.-H.; Song, J.; Xu, H.-C. J. Am. Chem. Soc. 2018, 140, 2460.
  (c) Qian, X.-Y.; Li, S.-Q.; Song, J.; Xu, H.-C. ACS Catal. 2017, 2730.
  (d) Cai, C.-Y.; Xu, H.-C. Nat. Commun. 2018, 9, 3551.
  (e) Hou, Z.-W.; Yan, H.; Song, J.-S.; Xu, H.-C. Chin. J. Chem. 2018, 36, 909.
  (f) Xiong, P.; Xu, H.-H.; Song, J.; Xu, H.-C. J. Am. Chem. Soc. 2018, 140, 2460.
  (g) Zhao, H.-B.; Xu, P.; Song, J.; Xu, H.-C. Angew. Chem., Int. Ed. 2018, 57, 15153.
  (h) Wu, Z.-J.; Li, S.-R.; Xu, H.-C. Angew. Chem., Int. Ed. 2018, 57, 14070.
  (i) Xu, F.; Li, Y.-J.; Huang, C.; Xu, H.-C. ACS Catal. 2018, 3820.
  (j) Hou, Z. W.; Mao, Z. Y.; Zhao, H. B.; Melcamu, Y. Y.; Lu, X.; Song, J.; Xu, H.-C. Angew. Chem., Int. Ed. 2016, 55, 9168.
  (k) Wu, Z.-J.; Li, S.-R.; Long, H.; Xu, H.-C. Chem. Commun. 2018, 54, 4601.
  (l) Hou, Z.-W.; Mao, Z.-Y.; Song, J.; Xu, H.-C. ACS Catal. 2017, 5810.
8. [8]
  (a) Gieshoff, T.; Kehl, A.; Schollmeyer, D.; Moeller, K. D.; Waldvogel, S. R. J. Am. Chem. Soc. 2017, 139, 12317.
  (b) Gieshoff, T.; Schollmeyer, D.; Waldvogel, S. R. Angew. Chem., Int. Ed. 2016, 55, 9437.
1. [1]
  Yuemin Chen , Yunqi Wu , Guoao Wang , Feihu Cui , Haitao Tang , Yingming Pan . Electricity-driven enantioselective cross-dehydrogenative coupling of two C(sp³)-H bonds enabled by organocatalysis. Chinese Chemical Letters, 2024, 35(9): 109445-. doi: 10.1016/j.cclet.2023.109445
2. [2]
  Jun Guo , Zhenbang Zhuang , Wanqiang Liu , Gang Huang . "Co-coordination force" assisted rigid-flexible coupling crystalline polymer for high-performance aqueous zinc-organic batteries. Chinese Chemical Letters, 2024, 35(9): 109803-. doi: 10.1016/j.cclet.2024.109803
3. [3]
  Zeyu Jiang , Yadi Wang , Changwei Chen , Chi He . Progress and challenge of functional single-atom catalysts for the catalytic oxidation of volatile organic compounds. Chinese Chemical Letters, 2024, 35(9): 109400-. doi: 10.1016/j.cclet.2023.109400
4. [4]
  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
5. [5]
  Jia-Ru Li , Ning Li , Li-Ling He , Jun He . Fluorine-functionalized zirconium-organic cages for efficient photocatalytic oxidation of thioanisole. Chinese Chemical Letters, 2025, 36(1): 109934-. doi: 10.1016/j.cclet.2024.109934
6. [6]
  Haoting Wang , Mengfan Luo , Yuzhong Wang , Jialong Yin , Heng Zhang , Jia Zhao , Bo Lai . Mn(Ⅱ) enhanced permanganate oxidation of trace organic pollutants in water: Critical role of in situ formation of colloidal MnO₂. Chinese Chemical Letters, 2025, 36(6): 110348-. doi: 10.1016/j.cclet.2024.110348
7. [7]
  Bofeng Li , Yuxian Wang , Ya Liu , Zhe Han , Tiantian Xing , Yumin Zhang , Chunmao Chen . Design and engineering strategies of porous carbonaceous catalysts toward activation of peroxides for aqueous organic pollutants oxidation. Chinese Chemical Letters, 2025, 36(6): 110374-. doi: 10.1016/j.cclet.2024.110374
8. [8]
  Kun Tang , Fen Su , Shijie Pan , Fengfei Lu , Zhongfu Luo , Fengrui Che , Xingxing Wu , Yonggui Robin Chi . Enones from aldehydes and alkenes by carbene-catalyzed dehydrogenative couplings. Chinese Chemical Letters, 2024, 35(9): 109495-. doi: 10.1016/j.cclet.2024.109495
9. [9]
  Fei Yin , Erli Yang , Xue Ge , Qian Sun , Fan Mo , Guoqiu Wu , Yanfei Shen . Coupling WO₃₋_x dots-encapsulated metal-organic frameworks and template-free branched polymerization for dual signal-amplified electrochemiluminescence biosensing. Chinese Chemical Letters, 2024, 35(4): 108753-. doi: 10.1016/j.cclet.2023.108753
10. [10]
  Weixu Li , Yuexin Wang , Lin Li , Xinyi Huang , Mengdi Liu , Bo Gui , Xianjun Lang , Cheng Wang . Promoting energy transfer pathway in porphyrin-based sp2 carbon-conjugated covalent organic frameworks for selective photocatalytic oxidation of sulfide. Chinese Journal of Structural Chemistry, 2024, 43(7): 100299-100299. doi: 10.1016/j.cjsc.2024.100299
11. [11]
  Shuai Liu , Wen Wu , Peili Zhang , Yunxuan Ding , Chang Liu , Yu Shan , Ke Fan , Fusheng Li . Mechanistic insights into acidic water oxidation by Mn(2,2′-bipyridine-6,6′-dicarboxylate)-based hydrogen-bonded organic frameworks. Chinese Journal of Structural Chemistry, 2025, 44(3): 100535-100535. doi: 10.1016/j.cjsc.2025.100535
12. [12]
  Wen-Bo Wei , Qi-Long Zhu . Electrosynthesis of hydroxylamine from earth-abundant small molecules. Chinese Journal of Structural Chemistry, 2025, 44(1): 100383-100383. doi: 10.1016/j.cjsc.2024.100383
13. [13]
  Lei Zhang , Chenyang Kou , Kun Ni , Yiwen Chen , Tongchuan Zhang , Baoliang Zhang . Microenvironment regulation of copper sites by chelating hydrophobic polymer for electrosynthesis of ethylene. Chinese Chemical Letters, 2025, 36(6): 110836-. doi: 10.1016/j.cclet.2025.110836
14. [14]
  Yue Zhang , Xiaoya Fan , Xun He , Tingyu Yan , Yongchao Yao , Dongdong Zheng , Jingxiang Zhao , Qinghai Cai , Qian Liu , Luming Li , Wei Chu , Shengjun Sun , Xuping Sun . Ambient electrosynthesis of urea from carbon dioxide and nitrate over Mo₂C nanosheet. Chinese Chemical Letters, 2024, 35(8): 109806-. doi: 10.1016/j.cclet.2024.109806
15. [15]
  Xuyun Lu , Yanan Chang , Shasha Wang , Xiaoxuan Li , Jianchun Bao , Ying Liu . Hydrogen peroxide electrosynthesis via two-electron oxygen reduction: From pH effect to device engineering. Chinese Chemical Letters, 2025, 36(5): 110277-. doi: 10.1016/j.cclet.2024.110277
16. [16]
  Xinlong Han , Huiying Zeng , Chao-Jun Li . Trifluoromethylative homo-coupling of carbonyl compounds. Chinese Chemical Letters, 2025, 36(1): 109817-. doi: 10.1016/j.cclet.2024.109817
17. [17]
  Xinghui Yao , Zhouyu Wang , Da-Gang Yu . Sustainable electrosynthesis: Enantioselective electrochemical Rh(III)/chiral carboxylic acid-catalyzed oxidative CH cyclization coupled with hydrogen evolution reaction. Chinese Chemical Letters, 2024, 35(9): 109916-. doi: 10.1016/j.cclet.2024.109916
18. [18]
  Qijun Tang , Wenguang Tu , Yong Zhou , Zhigang Zou . High efficiency and selectivity catalyst for photocatalytic oxidative coupling of methane. Chinese Journal of Structural Chemistry, 2023, 42(12): 100170-100170. doi: 10.1016/j.cjsc.2023.100170
19. [19]
  Kongchuan Wu , Dandan Lu , Jianbin Lin , Ting-Bin Wen , Wei Hao , Kai Tan , Hui-Jun Zhang . Elucidating ligand effects in rhodium(Ⅲ)-catalyzed arene–alkene coupling reactions. Chinese Chemical Letters, 2024, 35(5): 108906-. doi: 10.1016/j.cclet.2023.108906
20. [20]
  Shengkai Li , Yuqin Zou , Chen Chen , Shuangyin Wang , Zhao-Qing Liu . Defect engineered electrocatalysts for C–N coupling reactions toward urea synthesis. Chinese Chemical Letters, 2024, 35(8): 109147-. doi: 10.1016/j.cclet.2023.109147

Get Citation

PDF

XML

Metrics

PDF Downloads(40)
Abstract views(1185)
HTML views(163)

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