Citation: Xu Linlin, Xu Hui, Lin Haixia, Dai Huixiong. Progress in the Synthesis of Primary Anilines via C-H Bond Functionalization[J]. Chinese Journal of Organic Chemistry, ;2018, 38(8): 1940-1948. doi: 10.6023/cjoc201804004 shu

Progress in the Synthesis of Primary Anilines via C-H Bond Functionalization

Xu Linlin ^a ,
Xu Hui ^c ,
Lin Haixia ^a,, ,
Dai Huixiong ^b,,

a.
Department of Chemistry, Innovative Drug Research Center, Shanghai University, Shanghai 200444
b.
bDepartment of Medicinal Chemistry, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai, 201203
c.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Corresponding author: Lin Haixia, haixialin@staff.shu.edu.cn Dai Huixiong, xdai@sioc.ac.cn
Received Date: 2 April 2018
Revised Date: 23 April 2018
Available Online: 3 August 2018
Fund Project: the National Natural Science Foundation of China 21772211Project supported by the National Natural Science Foundation of China (No. 21772211) and the Youth Innovation Promotion Association of Chinese Academy of Sciences (No. 2014229)the Youth Innovation Promotion Association of Chinese Academy of Sciences 2014229

Figures(11)

Primary anilines are widely used in pharmaceutical, agrochemicals and material chemistry. In recent years, the green and efficient methods for constructing carbon-nitrogen (C-N) bonds to introduce primary amines has been one of the hottest topics in chemical synthesis. The direct C-H primary amination of aromatic compounds have received considerable attention due to its high efficiency and practicality. The recent progress in the C-H primary amination of aromatic compounds reactions is reviewed. Furthermore, the synthetic challenge and prospect in the future development for the synthesis of primary anilines through direct C-H amination are summarized.
- amination,
- C-H bond functionalization,
- primary anilines,
- transition-metal catalyzed
1. [1]
  (a) Ricci, A. Amino Group Chemistry: From Synthesis to the Life Sciences, Wiley-VCH, Weinheim, 2008.
  (b) Evano, G. ; Theunissen, C. ; Pradal, A. Nat. Prod. Rep. 2013, 30, 1467.
  (c) Okano, K. ; Tokuyama, H. ; Fukuyama, T. Chem. Commun. 2014, 50, 13650.
  (d) Quintas-Cardama, A. ; Kantarjian, H. ; Cortes, J. Nat. Rev. Drug Discovery 2007, 6, 834.
  (e) Uno, S. ; Kamiya, M. ; Yoshihara, T. ; Sugawara, K. ; Okabe, K. ; Tarhan, M. C. ; Fujita, H. ; Funatsu, T. ; Okada, Y. ; Tobita, S. ; Urano, Y. Nat. Chem. 2014, 6, 681.
  (f) Uno, S. ; Kamiya, M. ; Yoshihara, T. ; Sugawara, K. ; Okabe, K. ; Tarhan, M. C. ; Fujita, H. ; Funatsu, T. ; Okada, Y. ; Tobita, S. ; Urano, Y. Nat. Chem. 2014, 6, 681.
2. [2]
  (a) Lawrence, S. A. Amines: Synthesis Properties and Applications, Cambridge University Press, Cambridge, 2004.
  (b) Rappoport, Z. The Chemistry of Anilines, Parts 1 and 2, John Wiley & Sons, New York, 2007.
  (c) Aniszewski, T. Alkaloids. Secrets of Life, Elsevier Science, Amsterdam, 2007.
3. [3]
  (a) Sandmeyer, T. ; Ber. Dtsch. Chem. Ges. 1884, 17, 1633.
  (b) Hodgson, H. H. Chem. Rev. 1947, 40, 251.
  (c) Mo, F. ; Jiang, Y. ; Qiu, D. ; Zhang, Y. ; Wang, J. Angew. Chem., Int. Ed. 2010, 49, 1846.
  (d) Dai, J. ; Fang, C. ; Xiao, B. ; Yi, J. ; Xu, J. ; Liu, Z. ; Lu, X. ; Liu, L. ; Fu, Y. J. Am. Chem. Soc. 2013, 135, 8436.
  (e) Mo, F. ; Dong, G. ; Zhang, Y. ; Wang, J. Org. Biomol. Chem. 2013, 11, 1582.
4. [4]
  Porter, R. J.; Nohria, V.; Rundfeldt, C. Neurotherapeutics 2007, 4, 149. doi: 10.1016/j.nurt.2006.11.012
5. [5]
  Weijlard, J.; Orahoyats, P. D.; Jr, A. P. S.; Purdue, G.; Heath, F. K.; Pfister, K. J. Am. Chem. Soc. 1956, 78, 2342. doi: 10.1021/ja01591a088
6. [6]
  Yang, L. P.; Mccormack, P. L. Drugs 2011, 71, 221. doi: 10.2165/11205870-000000000-00000
7. [7]
  Bartlett, J. B.; Dredge, K.; Dalgleish, A. G. Nat. Rev. Cancer 2004. 4, 314. doi: 10.1038/nrc1323
8. [8]
  (a) Trost, B. Science (Washington, D. C. ) 1991, 254, 1471.
  (b) Wender, P. A. ; Verma, V. A. ; Paxton, T. J. ; Pillow, T. H. Acc. Chem. Res. 2008, 41, 40.
  (c) Young, I. S. ; Baran, P. S. Nat. Chem. 2009, 1, 193.
  (d) Afagh, N. A. ; Yudin, A. K. Angew. Chem., Int. Ed. 2010, 49, 262.
  (e) Zhu, L. ; Guo, B. ; Tang, D. ; Hu, X. ; Li, G. Hu, C. J. Catal. 2007, 245, 446.
  (g) Singha, S. ; Parida, K. M. Catal. Sci. Technol. 2011, 1, 1496.
  (h) Parida, K. M. ; Rath, D. ; Dash, S. S. J. Mol. Catal. A: Chem. 2010, 318, 85.
9. [9]
  Smith, M. B.; March, J. March's Advanced Organic Chemistry:Reactions, Mechanisms and Structure, 6th ed., John Wiley & Sons, Hoboken, 2007.
10. [10]
  (a) Ullmann, F. Ber. 1903, 36, 2382.
  (b) Goldberg, I. Ber. 1906, 39, 1691.
11. [11]
  (a) Kosugi, M. ; Kameyama, M. ; Migita, T. Chem. Lett. 1983, 927.
  (b) Guram, A. S. ; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 7901.
  (c) Paul, F. ; Patt, J. ; Hartwig, J. F. J. Am. Chem. Soc. 1994, 116, 5969.
12. [12]
  (a) Chan, D. ; Monaco, K. ; Wang, R. ; Winter, M. Tetrahedron Lett. 1998, 39, 2933.
  (b) Evans, D. ; Katz, J. ; West, T. Tetrahedron Lett. 1998, 39, 2937.
  (c) Lam, P. ; Clark, C. ; Saubern, S. ; Adams, J. ; Winters, M. ; Chan, D. ; Combs, A. Tetrahedron Lett. 1998, 39, 2941.
13. [13]
  (a) Chen, X. ; Engle, K. M. ; Wang, D.-H. ; Yu, J.-Q. Angew. Chem. Int. Ed. 2009, 121, 5196.
  (b) Daugulis, O. ; Do, H.-Q. ; Shabashov, D. Acc. Chem. Res. 2009, 42, 1074.
  (c) Lyons, T. W. ; Sanford, M. S. Chem. Rev. 2010, 110, 1147
14. [14]
  (a) Davies, H. M. L. ; Long, M. S. Angew. Chem., Int. Ed. 2005, 44, 3518.
  (b) Cho, S. H. ; Kim, J. Y. ; Kwak, J. ; Chang, S. Chem. Soc. Rev. 2011, 40, 5068.
  (c) Tsang, W. C. P. ; Zheng, N. ; Buchwald, S. L. J. Am. Chem. Soc. 2005, 127, 14560.
  (d) Wasa, M. ; Yu, J.-Q. J. Am. Chem. Soc. 2008, 130, 14058.
  (e) Hamada, T. ; Ye, X. ; Stahl, S. S. J. Am. Chem. Soc. 2008, 130, 833.
  (f) Matsuda, N. ; Hirano, K. ; Satoh, T. ; Miura, M. Org. Lett. 2011, 13, 2860.
  (g) Li, G. ; Jia, C. ; Sun, K. Org. Lett. 2013, 15, 5198.
  (h) Shang, M. ; Sun, S.-Z. ; Zeng, S.-H. ; Dai, H.-X. ; Yu, J.-Q. Org. Lett. 2013, 15, 5286.
  (i) Brasche, G. ; Buchwald, S. L. ; Angew. Chem., Int. Ed. 2008, 47, 1932.
  (j) Roane, J. ; Daugulis, O. J. Am. Chem. Soc. 2016, 138, 4601.
  (h)Wang, F. ; Jin, L. ; Kong, L.-H. ; Li, X.-W. Org. Lett. 2017, 19, 1812.
15. [15]
  (a) Amaoka, Y. ; Kamijo, S. ; Hoshikawa, T. ; Inoue, M. J. Org. Chem. 2012, 77, 9959.
  (b) Foo, K. ; Sella, E. ; Thome, I. ; Eastgate, M. D. ; Baran, P. S. J. Am. Chem. Soc. 2014, 136, 5279.
  (c) Zhou, L. ; Tang, S. ; Qi, X. ; Lin, C. ; Liu, K. ; Lan Y. ; Lei, A. Org. Lett. 2014, 16, 3404.
  (d) Allen, L. J. ; Cabrera, P. J. ; Cabrera, M. Lee; Sanford, M. S. J. Am. Chem. Soc. 2014, 136, 5607.
  (e) Hwang, Y. ; Park, Y. ; Chang, S. Chem.-Eur. J. 2017, 23, 11147.
  (f) Hong, S. Y. ; Park, Y. ; Hwang, Y. ; Kim, Y. B. ; Baik, M. H. ; Chang, S. Science 2018, 359, 1016.
16. [16]
17. [17]
  Graebe, C. Ber. 1901, 34, 1778. doi: 10.1002/(ISSN)1099-0682
18. [18]
  Jaubert, G. E'. Comp. Rend. 1901, 132, 841.
19. [19]
  Kovacic, P.; Bennett, R. P. J. Am. Chem. Soc. 1961, 83, 221. doi: 10.1021/ja01462a043
20. [20]
  Yuzawa, H.; Yoshida, H. Chem. Commun. 2010, 46, 8854. doi: 10.1039/c0cc03551c
21. [21]
  (a) Yu, T. ; Yang, R. ; Xia, S. ; Li, G. ; Hu, C. Catal. Sci. Technol. 2014, 4, 3159.
  (b) Yu, T. ; Zhang, Q. ; Xia, S. ; Li, G. ; Hu, C. Catal. Sci. Technol. 2014, 4, 639.
22. [22]
  Paudyal, M. P.; Adebesin, A. M.; Burt, S. R.; Ess, D. H.; Ma, Z.; Kürti, L.; Falck, J. R. Science (Washington, D. C.) 2016, 353, 1144.
23. [23]
  Legnani, L.; Prina Cerai, G.; Morandi, B. ACS Catal. 2016, 6, 8162. doi: 10.1021/acscatal.6b02576
24. [24]
  Yi, H.; Zhang, G.; Wang, H.; Huang, Z.; Wang, J.; Singh, A. K; Lei, A. Chem. Rev. 2017, 117, 9016. doi: 10.1021/acs.chemrev.6b00620
25. [25]
  Citterio, A.; Gentile, A.; Minisci, F.; Navarrini, V.; Serravalle, M.; Ventura, S. J. Org. Chem. 1984, 49, 4479. doi: 10.1021/jo00197a030
26. [26]
  Morofuji, T.; Shimizu, A.; Yoshida, J.-I. J. Am. Chem. Soc. 2013, 135, 5000. doi: 10.1021/ja402083e
27. [27]
  Morofuji, T.; Shimizu, A.; Yoshida, J.-I. Chem.-Eur. J. 2015, 21, 3211. doi: 10.1002/chem.v21.8
28. [28]
  Kim, H.; Kim, T.; Lee, D. G.; Roh, S. W.; Lee, C. Chem. Commun. 2014, 50, 9273. doi: 10.1039/C4CC03905J
29. [29]
  Romero, N. A.; Margrey, K. A.; Tay, N. E.; Nicewicz, D. A. Science (Washington, D. C.) 2015, 349, 1326. doi: 10.1126/science.aac9895
30. [30]
  Zheng, Y.-W.; Chen, B.; Ye, P.; Feng, K.; Wang, W.; Meng, Q.-Y.; Wu, L.-Z.; Tung, C.-H. J. Am. Chem. Soc. 2016, 138, 10080. doi: 10.1021/jacs.6b05498
31. [31]
  Liu, J.-Z.; Wu, K.; Shen, T.; Liang, Y.-J.; Zou, M.-C.; Zhu, Y.-C.; Li, X. W.; Li, X.-Y.; Jiao, N. Chem.-Eur. J. 2017, 23, 563. doi: 10.1002/chem.201605476
32. [32]
  (a) Kakiuchi, F. ; Sekine, S. ; Kamatani, A. ; Sonoda, M. ; Chatani, N. ; Murai, S. Bull. Chem. Soc. Jpn. 1995, 68, 62.
  (b) Giri, R. ; Shi, B.-F. ; Engle, K. M. ; Maugel, N. ; Yu, J.-Q. Chem. Soc. Rev. 2009, 38, 3242.
  (c) Colby, D. A. ; Bergman, R. G. ; Ellman, J. A. Chem. Rev. 2010, 110, 624.
  (d) Wencel-Delord, J. ; Dröge, T. ; Liu, F. ; Glorius, F. Chem. Soc. Rev. 2011, 40, 4740.
  (g) Arockiam, P. B. ; Bruneau, C. ; Dixneuf, P. H. Chem. Rev. 2012, 112, 5879.
33. [33]
  (a) Liu, J.-D. ; Chen, G.-S; Tan Z. Adv. Synth. Catal. 2016, 358, 1174.
  (b) Jiao, J. ; Murakami, K. ; Itami, K. ACS Catal. 2016, 6, 610.
  (c) Park, Y. ; Kim, Y. ; Chang, S. Chem. Rev. 2017, 117, 9247.
34. [34]
  (a) Chen, X. ; Hao, X.-S. ; Goodhue, C. E. ; Yu, J.-Q. J. Am. Chem. Soc. 2006, 128, 6790.
  (b) Rao, W.-H. ; Shi, B.-F. Org. Chem. Front. 2016, 3, 1028.
  (c) Shang, M. ; Sun, S.-Z. ; Wang, M.-M. ; Dai, H.-X. Synthesis 2016, 48, 4381.
35. [35]
  Peng, J.; Chen, M.; Xie, Z.; Luo, S.; Zhu, Q. Org. Chem. Front. 2014, 1, 777. doi: 10.1039/C4QO00143E
36. [36]
  Yu, L.; Chen, X.; L, D; Tan, Z.; Gui, Q.-W. Adv. Synth. Catal. 2018, 360, 1346. doi: 10.1002/adsc.v360.7
37. [37]
  Yu, S.-J.; Wan, B.-S.; Li, X.-W. Org. Lett. 2013, 15, 3706. doi: 10.1021/ol401569u
38. [38]
  Raghuvanshi, K.; Zell, D.; Rauch, K.; Ackermann, L. ACS Catal. 2016, 6, 3172 doi: 10.1021/acscatal.6b00711
39. [39]
  Li, Z.; Yu, H.; Bolm, C. Angew. Chem., Int. Ed. 2017, 56, 9532. doi: 10.1002/anie.v56.32
40. [40]
  Tezuka, N.; Shimojo, K.; Komagawa, S.; Miyamoto, K.; Saito, T.; Takita, R.; Uchiyama, M. J. Am. Chem. Soc. 2016, 138, 9166. doi: 10.1021/jacs.6b03855
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