Citation: Wang Yunlong, Zhang Linbao, Niu Junlong, Song Maoping. Copper-Promoted Direct Nitration of Arenes Assisted by an N, O-Bidentate Directing System[J]. Chinese Journal of Organic Chemistry, ;2019, 39(6): 1761-1766. doi: 10.6023/cjoc201901015 shu

Copper-Promoted Direct Nitration of Arenes Assisted by an N, O-Bidentate Directing System

a.
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001
b.
College of Chemistry and Molecular Engineering, Qingdao University of Science & Technology, Qingdao 266042

Corresponding author: Niu Junlong, niujunlong@zzu.edu.cn Song Maoping, mpsong@zzu.edu.cn
Received Date: 11 January 2019
Revised Date: 25 February 2019
Available Online: 8 June 2019
Fund Project: the Program for Science & Technology Innovation Talents in Universities of Henan Province 19HASTIT038Project supported by the National Natural Science Foundation of China (Nos. 21772179, 21672192), the Program for Science & Technology Innovation Talents in Universities of Henan Province (No. 19HASTIT038)the National Natural Science Foundation of China 21672192the National Natural Science Foundation of China 21772179

Figures(3)

Cu(Ⅱ)-promoted C-H nitration of arenes has been disclosed with the aid of N, O-bidentate directing group. The protocol was operationally simple by using NaNO₂as the nitration source. Various amide substrates were tolerated in the reaction system, which establishes opportunities for developing simple and facile methods, and enriches the strategies to access aromatic nitro derivatives.
- C-H activation,
- bidentate direction,
- Cu-catalyzed,
- nitration
1. [1]
  (a) Olah, G. A.; Malhotra, R.; Narang, S. C. Nitration: Methods and Mechanisms, Wiley-VCH, Weinheim, 1989.
  (b) Feuer, H.; Nielsen, A. T. Nitro Compounds: Recent Advances in Synthesis and Chemistry, Wiley-VCH, Weinheim, 1990.
2. [2]
  (a) Schofield, K. Aromatic Nitrations, Cambridge University Press, Cambridge, 1980.
  (b) Ono, N. The Nitro Group in Organic Synthesis, Wiley-VCH, Weinheim, 2001.
3. [3]
  Hearn, R.; Russell, M. K. R. G. Ann. Rheum. Dis. 1983, 42(Suppl.), 39.
4. [4]
  (a) Tani, K.; Lukin, K.; Eaton, P. E. J. Am. Chem. Soc. 1997, 119, 6.
  (b) Salzbrunn, S.; Simon, J.; Prakash, G. K. S.; Petasis, N. A.; Olah, G. A. Synlett 2000, 1485.
  (c) Prakash, G. K. S.; Panja, C.; Mathew, T.; Surampudi, V.; Petasis, N. A.; Olah, G. A. Org. Lett. 2004, 6, 2205.
  (d) Yan, G.; Yang, M. Org. Biomol. Chem. 2013, 11, 2554.
  (e) Das, J. P.; Sinha, P.; Roy, S. Org. Lett. 2002, 4, 3055.
5. [5]
  (a) Kakiuchi, F.; Chatani, N. Adv. Synth. Catal. 2003, 345, 1077.
  (b) Ackermann, L.; Vicente, R.; Kapdi, A. R. Angew. Chem., Int. Ed. 2009, 48, 9792.
  (c) Satoh, T.; Miura, M. Chem.-Eur. J. 2010, 16, 11212.
  (d) Wencel-Delord, J.; Drö ge, T.; Liu, F.; Glorius, F. Chem. Soc. Rev. 2011, 40, 4740.
  (e) Chen, X.; Engle, K. M.; Wang, D.-H.; Yu, J.-Q. Angew. Chem. Int. Ed. 2009, 48, 5094.
  (f) Ackermann, L. Acc. Chem. Res. 2014, 47, 281.
  (g) Misal Castro, L. C.; Chatani, N. Chem. Lett. 2015, 44, 410.
  (h) Satoh, T.; Miura, M. Chem. Lett. 2006, 36, 200.
6. [6]
  (a) Liu, Y.-K.; Lou, S.-J.; Xu, D.-Q.; Xu, Z.-Y. Chem.-Eur. J. 2010, 13590.
  (b) Zhang, W.; Lou, S.; Liu, Y.; Xu, Z. J. Org. Chem. 2013, 78, 5932.
  (c) Zhang, L.; Liu, Z.; Li, H.; Fang, G.; Barry, B. D.; Belay, T. A.; Bi, X.; Liu, Q. Org. Lett. 2011, 13, 6536.
  (d) Zhang, H.; Zhao, L.; Wang, D.-X.; Wang, M.-X. Org. Lett. 2013, 15, 3836.
  (e) Xie, F.; Qi, Z.; Li, X. Angew. Chem., Int. Ed. 2013, 52, 11862.
  (f) Hernando, E.; Castillo, R. R.; Rodrĭguez, N.; Arrayás, R. G.; Carretero, J. C. Chem. Eur. J. 2014, 20, 13854.
  (g) Kianmehr, E.; Nasab, S. B. Eur. J. Org. Chem. 2018, 6447.
  (h) Katayev, D.; Pfister, K. F.; Wendling, T.; Gooβen, L. J. Chem.-Eur. J. 2014, 20, 9902.
  (i) Liu, J.; Zhuang, S.; Gui, Q.; Chen, X.; Yang, Z.; Tan, Z. Adv. Synth. Catal. 2015, 357, 732.
7. [7]
  Zaitsev, V. G.; Shabashov, D.; Daugulis, O. J. Am. Chem. Soc. 2005, 13154.
8. [8]
  Selected examples.
  (a) Asako, S.; Ilies, L.; Nakamura, E. J. Am. Chem. Soc. 2013, 135, 17755.
  (b) Shang, R.; Ilies, L.; Matsumoto, A.; Nakamura, E. J. Am. Chem. Soc. 2013, 135, 6030.
  (c) Fruchey, E. R.; Monks, B. M.; Cook, S. P. J. Am. Chem. Soc. 2014, 136, 13130.
9. [9]
  Selected examples.
  (a) Grigorjeva, L.; Daugulis, O. Angew. Chem., Int. Ed. 2014, 53, 10209.
  (b) Grigorjeva, L.; Daugulis, O. Org. Lett. 2014, 16, 4684.
  (c) Grigorjeva, L.; Daugulis, O. Org. Lett. 2014, 16, 4688.
  (d) Ma, W.; Ackermann, L. ACS Catal.2015, 5, 2822.
  (e) Zhang, L.-B.; Hao, X.-Q.; Zhang, S.-K.; Liu, Z.-J.; Zheng, X.-X.; Gong, J.-F.; Niu, J.-L.; Song, M.-P. Angew. Chem., Int. Ed. 2015, 54, 272.
  (f) Zhang, L.-B.; Hao, X.-Q.; Zhang, S.-K.; Zheng, X.-X.; Liu, Z.-J.; Gong, J.-F.; Niu, J.-L.; Song, M.-P. Angew. Chem., Int. Ed. 2015, 54, 10012.
  (g) Saxena, P.; Kapur, M. Chem. Asian J. 2018, 13. 861.
10. [10]
  Selected examples:
  (a) Aihara, Y.; Chatani, N. J. Am. Chem. Soc. 2014, 136, 898.
  (b) Song, W.; Lackner, S.; Ackermann, L. Angew. Chem., Int. Ed. 2014, 53, 2477.
  (c) Shiota, H.; Ano, Y.; Aihara, Y.; Fukumoto, Y.; Chatani, N. J. Am. Chem. Soc. 2011, 133, 14952.
11. [11]
  Selected examples.
  (a) Tran, L. D.; Popov, I.; Daugulis, O. J. Am. Chem. Soc. 2012, 134, 18237.
  (b) Truong, T.; Klimovica, K.; Daugulis, O. J. Am. Chem. Soc. 2013, 135, 9342.
  (c) Tran, L. D.; Roane, J.; Daugulis, O. Angew. Chem., Int. Ed. 2013, 52, 6043.
  (d) Roane, J.; Daugulis, O. Org. Lett. 2013, 15, 5842.
  (e) Shang, M.; Sun, S.-Z.; Wang, H.-L.; Laforteza, B. N.; Dai, H.-X.; Yu, J.-Q. Angew. Chem., Int. Ed. 2014, 53, 10439.
  (f) Shang, M.; Wang, H.-L.; Sun, S.-Z.; Dai, H.-X.; Yu, J.-Q. J. Am. Chem. Soc. 2014, 136, 11590.
  (g) Li, X.; Liu, Y.-H.; Gu, W.-J.; Li, B.; Chen, F.-J.; Shi, B.-F. Org. Lett. 2014, 16, 3904.
  (h) Dong, J.; Wang, F.; You, J. Org. Lett. 2014, 16, 2884.
  (i) Nishino, M.; Hirano, K.; Satoh, T.; Miura, M. Angew. Chem., Int. Ed. 2013, 52, 4457.
  (j) Chen, F.-J.; Liao, G.; Li, X.; Wu, J.; Shi, B.-F. Org. Lett. 2014, 16, 5644.
  (k) Rouquet, G.; Chatani, N. Angew. Chem., Int. Ed. 2013, 52, 11726.
  (l) Zhang, Q.; Chen, K.; Shi, B.-F. Synlett 2014, 25, 1941.
  (m) Daugulis, O.; Roane, J.; Tran, L. D. Acc. Chem. Res. 2015, 48, 1053.
  (n) Dou, Y.-D.; Yin, B.; Zhang, P.-F.; Zhu, Q. Eur. J. Org. Chem. 2018, 4571.
  (o) Wang, C.-M.; Tang, K.-X.; Gao, T.-H.; Chen, L.; Sun, L.-P. J. Org. Chem. 2018, 83, 8315.
  (p) Tu, D.-Q.; Luo, J.; Jiang, C. Chem. Commun. 2018, 54, 2514.
  (q) Vinayak, B.; Chandrasekharam, M. Org. Lett. 2017, 19, 3528.
12. [12]
  Selected our recent reports: (a) Hao, X.-Q.; Chen, L.-J.; Ren, B.; Li, L.-Y.; Yang, X.-Y.; Gong, J.-F.; Niu, J.-L.; Song, M.-P. Org. Lett. 2014, 16, 1104.
  (b) Zhang, L.-B.; Hao, X.-Q.; Zhang, S.-K.; Liu, K.; Ren, B.; Gong, J.-F.; Niu, J.-L.; Song, M.-P. J. Org. Chem. 2014, 79, 10399.
13. [13]
  Selected examples.
  (a) Wang, D.-W.; Zhao, K.-Y.; Xu, C.-Y.; Miao, H.-Y.; Ding, Y.-Q. ACS Catal. 2014, 4, 3910.
  (b) Wang, D.-W.; Ge, B.-Y.; Li, L.; Shan, J.; Ding, Y.-Q. J. Org. Chem. 2014, 79, 8607.
  (c) Guo, X-K.; Zhang, L.-B.; Wei, D.-H.; Niu, J.-L. Chem. Sci. 2015, 6, 7059.
  (d) Wang, D.-W.; Yu, X.; Yao, W.; Hu, W.-K.; Ge, C.-Y.; Shi, X.-D. Chem.-Eur. J. 2016, 22, 55433.
  (e) Yu, X.-L.; Wang, D.-S.; Xu, Z.-J.; Yang, B.-B.; Wang, D.-W. Org. Chem. Front. 2017, 4, 1011.
  (f) Wu, Q.; Pan, L.; Du, G.-M.; Zhang, C.; Wang, D.-W. Org. Chem. Front. 2018, 5, 2668.
  (g) Xu, Z.-J.; Yu, X.-L.; Sang, X.-X.; Wang, D.-W. Green Chem. 2018, 20, 2571.
  (h) Wang, Y.; Du, C.; Wang, Y.-Y.; Guo, X.-K.; Fang, Lei.; Song, M.-P.; Niu, J.-L.; Wei, D.-H. Adv. Synth. Catal. 2018, 360, 2668.
  (i) Wang, D.-W.; Yu, X.-L.; Ge, B.-Y.; Miao, H.-Y.; Ding, Y.-Q. Chin. J. Org. Chem. 2015, 35, 676.
  (j) Hu, X.-Y.; Yang, B.-B.; Yao, W.; Wang, D.-W. Chin. J. Org. Chem. 2018, 38, 3296.
14. [14]
  Suess, A. M.; Ertem, M. Z.; Cramer, C. J.; Stahl, S. S. J. Am. Chem. Soc. 2013, 135, 9797. doi: 10.1021/ja4026424
1. [1]
  Xiao Tang , Erik V. Van der Eycken , Liangliang Song . Transition metal-catalyzed C-H activation/annulation for the construction of unnatural amino acids and peptides. Chinese Chemical Letters, 2026, 37(2): 111678-. doi: 10.1016/j.cclet.2025.111678
2. [2]
  Wei-Bin Li , Xiao-Chao Huang , Pei Liu , Jie Kong , Guo-Ping Yang . Recent advances in directing group assisted transition metal catalyzed para-selective C-H functionalization. Chinese Chemical Letters, 2025, 36(6): 110543-. doi: 10.1016/j.cclet.2024.110543
3. [3]
  Chao Chen , Wenwen Yu , Guangen Huang , Xuelian Ren , Xiangli Chen , Yixin Li , Shenggui Liang , Mengmeng Xu , Mingyue Zheng , Yaxi Yang , He Huang , Wei Tang , Bing Zhou . Asymmetric macrocyclization enabled by Rh(Ⅲ)-catalyzed CH activation: Enantioenriched macrocyclic inhibitor of Zika virus infection. Chinese Chemical Letters, 2024, 35(11): 109574-. doi: 10.1016/j.cclet.2024.109574
4. [4]
  Xiang Huang , Dongzhen Xu , Yang Liu , Xia Huang , Yangfan Wu , Dongmei Fang , Bing Xia , Wei Jiao , Jian Liao , Min Wang . Asymmetric synthesis of difluorinated α-quaternary amino acids (DFAAs) via Cu-catalyzed difluorobenzylation of aldimine esters. Chinese Chemical Letters, 2024, 35(12): 109665-. doi: 10.1016/j.cclet.2024.109665
5. [5]
  Bowen Wang , Longwu Sun , Qianqian Cao , Xinzhi Li , Jianai Chen , Shizhao Wang , Miaolin Ke , Fener Chen . Cu-catalyzed three-component CSP coupling for the synthesis of trisubstituted allenyl phosphorothioates. Chinese Chemical Letters, 2024, 35(12): 109617-. doi: 10.1016/j.cclet.2024.109617
6. [6]
  Lianshun Zhang , Lan Bao , Ting Song , Shangying Qiao , Yifan Liu , Xianxiu Xu , Jinhuan Dong . Cu-catalyzed biheterocyclization along with sulfonyl remote migration: Access to Marinoquinoline alkaloids and 4-sulfonyl pyrrolo[2,3-c]quinolines. Chinese Chemical Letters, 2025, 36(10): 110915-. doi: 10.1016/j.cclet.2025.110915
7. [7]
  Junhua Li , Yu Fu , Yian Shi . A rapid access to fused polycyclic indolo[2,1-a]isoquinolins via Pd-catalyzed sequential Heck/C-H activation/amination reaction with diaziridinone. Chinese Chemical Letters, 2026, 37(3): 111376-. doi: 10.1016/j.cclet.2025.111376
8. [8]
  Shihaozhi Wang , Jia-Hui Shi , Shan Xu , Xue-Jing Zhang , Ming Yan . Palladium-catalyzed carbene C-H insertion reaction of non-activated arenes. Chinese Chemical Letters, 2026, 37(4): 111225-. doi: 10.1016/j.cclet.2025.111225
9. [9]
  Xin-Juan Wang , Yao-Hang Cheng , Xin-Yan Lv , Li-Ye Liang , Guang-Hui An , Guang-Ming Li . Ruthenium-catalyzed alkylarylation of alkenes via para-selective C-H functionalization of unprotected anilines. Chinese Chemical Letters, 2026, 37(8): 112154-. doi: 10.1016/j.cclet.2025.112154
10. [10]
  Shulei Hu , Yu Zhang , Xiong Xie , Luhan Li , Kaixian Chen , Hong Liu , Jiang Wang . Rh(Ⅲ)-catalyzed late-stage C-H alkenylation and macrolactamization for the synthesis of cyclic peptides with unique Trp(C7)-alkene crosslinks. Chinese Chemical Letters, 2024, 35(8): 109408-. doi: 10.1016/j.cclet.2023.109408
11. [11]
  Wujun Jian , Mong-Feng Chiou , Yajun Li , Hongli Bao , Song Yang . Cu-catalyzed regioselective diborylation of 1,3-enynes for the efficient synthesis of 1,4-diborylated allenes. Chinese Chemical Letters, 2024, 35(5): 108980-. doi: 10.1016/j.cclet.2023.108980
12. [12]
  Qiao Song , Xue Peng , Zhouyu Wang , Leyong Wang . Iron-catalyzed C–H activation: A sustainable approach to efficient organic synthesis. Chinese Chemical Letters, 2025, 36(5): 110869-. doi: 10.1016/j.cclet.2025.110869
13. [13]
  Weimei Zeng , Youai Qiu . Electrochemical C-H carboxylation of benzylamines. Chinese Chemical Letters, 2026, 37(1): 111679-. doi: 10.1016/j.cclet.2025.111679
14. [14]
  Taixin Yang , Yuanyuan Huang , Yingchao Dou , Yanbo Zhang , Baohe Yang , Dandan Yang , Jun-Long Niu . Atropisomeric synthesis of multiple C–N or N–N axially chiral calix[4]arenes through cobalt-catalyzed multisite C–H activation/annulation. Chinese Chemical Letters, 2026, 37(12): 112436-. doi: 10.1016/j.cclet.2026.112436
15. [15]
  Tian-Zhang Wang , Le-Yu Tang , Yu-Qiu Guan , Lingfei Hu , Gang Lu , Yu-Feng Liang . Nickel-catalyzed reductive alkynylation of ketoimines via unstrained C–C bond activation. Chinese Chemical Letters, 2025, 36(11): 111050-. doi: 10.1016/j.cclet.2025.111050
16. [16]
  Mengyao Yuan , Wansen Xie , Xiaoyu Yang . Enantioselective synthesis of inherently chiral calix[4]arenes via asymmetric C-H bromination of phenols. Chinese Chemical Letters, 2026, 37(9): 112157-. doi: 10.1016/j.cclet.2025.112157
17. [17]
  Yanjie Lv , Xinyu Zhao , Jing Sun , Huiying Sun , Wenxi Zhang , Yuhan Cui , Xiao Li , Zhongmin Su . Atomic-level regulation of POMOF homologous isomer for photocatalytic C-H bond oxidation. Chinese Chemical Letters, 2026, 37(10): 113018-. doi: 10.1016/j.cclet.2026.113018
18. [18]
  Xin Li , Jia-Min Lu , Bo Li , Chen Zhao , Bei-Bei Yang , Li Li . Chiroptical sensing for remote chiral amines via a C–H activation reaction. Chinese Chemical Letters, 2025, 36(5): 110310-. doi: 10.1016/j.cclet.2024.110310
19. [19]
  Yongli Zhao , Dingsheng Cao , Jie-Ping Wan , Yunyun Liu . Synthesis of 3-phosphinyl chromones via in situ iodination mediated C-H phosphination and the tunable synthesis of 2-phosphoryl chromanones. Chinese Chemical Letters, 2026, 37(1): 111740-. doi: 10.1016/j.cclet.2025.111740
20. [20]
  Jinpeng Du , Junlin Chen , Yulong Shan , Tongliang Zhang , Yu Sun , Zhongqi Liu , Xiaoyan Shi , Wenpo Shan , Yunbo Yu , Hong He . Insight into the effects of C₃H₆ on fresh and hydrothermally aged Cu-SSZ-39 catalysts. Chinese Chemical Letters, 2025, 36(3): 110019-. doi: 10.1016/j.cclet.2024.110019

Get Citation

PDF

XML

Metrics

PDF Downloads(11)
Abstract views(1569)
HTML views(162)

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