Citation: Liu Xueying, Liu Zhenwei, Guo Yuanyuan, Li Jingya, Zou Dapeng, Wu Yusheng, Wu Yangjie. One-Pot, Two-Step Reductive Amination of Boronate Ester Containing Aromatic Amines and Aldehydes Using B₂pin₂ as Reductant[J]. Chinese Journal of Organic Chemistry, ;2019, 39(7): 2001-2008. doi: 10.6023/cjoc201902011 shu

One-Pot, Two-Step Reductive Amination of Boronate Ester Containing Aromatic Amines and Aldehydes Using B₂pin₂ as Reductant

a.
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450052
b.
Tetranov Biopharm, Limited Liability Company, Zhengzhou 450052

Received Date: 13 February 2019
Revised Date: 15 March 2019
Available Online: 29 July 2019
Fund Project: Project supported by the National Natural Science Foundation of China (Nos. 21172200, 21702191)the National Natural Science Foundation of China 21172200the National Natural Science Foundation of China 21702191

Figures(2)

The aromatic amine functionality occupies a very important role in organic chemistry due to its prominence in biological and naturally occurring molecules. In addition, the synthesized secondary aromatic amines with pendant boronate ester are versatile intermediates in several organic transformations. The one-pot, two-step reductive amination of boron-containing primary aromatic amines and aldehydes has been achieved in the presence of NaOH in ethanol using B₂pin₂ as reductant. After extensive screening of various reaction parameters, such as base, reaction temperature, solvent, reaction time and protective gas, a series of secondary aromatic amines with pendant boronate ester and various functional groups were obtained in moderate to good yields under the optimal reaction conditions. This system features generally high yields and broad functional group tolerance. The boronate ester substituent is a very good handle to be further functionalized.
- reductive amination,
- boron-containing secondary aromatic amines,
- bis (pinacolato) diboron,
- aldehydes
1. [1]
  Pham, P. D.; Bertus, P.; Legoupy, S. Chem. Commun. 2009, 6207.
2. [2]
  For literature pertaining to the origins and definition of reductive amination, see:(a) Emerson, W. S. Org. React. 1948, 4, 174.
  (b) Moore, M. L. Org. React. 1949, 5, 301.
  (c) Nugenta, T. C.; El-Shazly, M. Adv. Synth. Catal. 2010, 352, 753.
3. [3]
  Chi, Y.; Zhou, Y.; Zhang, X. J. Org. Chem. 2003, 68, 4120. doi: 10.1021/jo026856z
4. [4]
  (a) Skucas, E.; Kong, J.; Krische, M. J. J. Am. Chem. Soc. 2007, 129, 7242.
  (b) Park, J. W.; Chung, Y. K. ACS Catal. 2015, 5, 4846.
5. [5]
  Pagnoux-Ozherelyeva, A.; Pannetier, N.; Mbaye, M. D.; Gaillard, S.; Renaud, J.-L. Angew. Chem., Int. Ed. 2012, 51, 4976. doi: 10.1002/anie.201201360
6. [6]
  Nasrollahzadeh, M. New J. Chem. 2014, 38, 5544. doi: 10.1039/C4NJ01440E
7. [7]
  Huang, L.; Wang, Z.; Geng, L.; Chen, R.; Xing, W.; Wang, Y.; Huang, J. RSC Adv. 2015, 5, 56936. doi: 10.1039/C5RA05243B
8. [8]
  Gao, G.; Sun, P.; Li, Y.; Wang, F.; Zhao, Z.; Qin, Y.; Li, F. ACS Catal. 2017, 7, 4927. doi: 10.1021/acscatal.7b01786
9. [9]
  Abdel-Magid, A. F.; Carson, K. G.; Harris, B. D.; Maryanoff, C. A.; Shah, R. D. J. Org. Chem. 1996, 61, 3849. doi: 10.1021/jo960057x
10. [10]
  Roe, A.; Montgomery, J. A. J. Am. Chem. Soc. 1953, 75, 910. doi: 10.1021/ja01100a040
11. [11]
  Tripathi, R. P.; Verma, S. S.; Pandey, J.; Tiwari, V. K. Curr. Org. Chem. 2008, 12, 1093. doi: 10.2174/138527208785740283
12. [12]
  (a) Borch, R. F.; Bernstein, M. D.; Durst, H. D. J. Am. Chem. Soc. 1971, 93, 2897.
  (b) Borch, R. F.; Hassid, A. I. J. Org. Chem. 1972, 37, 1673.
  (c) Marchini, P.; Liso, G.; Reho, A.; Liberatone, F.; Moracci, F. M. J. Org. Chem. 1975, 40, 3453.
  (d) Lane, C. F. Synthesis 1975, 135.
13. [13]
  (a) Abdel-Magid, A. F.; Maryanoff, C. A.; Carson, K. G. Tetrahedron Lett. 1990, 31, 5595.
  (b) Kim, H. O.; Carrol, B.; Lee, M. S. Synth. Commun. 1997, 27, 2505.
  (c) Tarasevich, V. A.; Kozlov, N. G. Russ. Chem. Rev. 1999, 68, 55.
14. [14]
  Borch, R. F.; Durst, H. D. J. Am. Chem. Soc. 1969, 91, 3996. doi: 10.1021/ja01042a078
15. [15]
  (a) Ros, A.; Fernandez, R.; Lassaletta, J. M. Chem. Soc. Rev. 2014, 43, 3229.
  (b) Hartwig, J. F. Acc. Chem. Res. 2012, 45, 864.
  (c) Hartwig, J. F. Chem. Soc. Rev. 2011, 40, 1992.
  (d) Mkhalid, I. A. I.; Barnard, J. H.; Marder, T. B.; Murphy, J. M.; Hartwig, J. F. Chem. Rev. 2010, 110, 890.
16. [16]
  (a) Xu, H.; Zhao, C.; Qian, Q.; Deng, W.; Gong, H. Chem. Sci. 2013, 4, 4022.
  (b) Yu, X.; Wang, S.; Xu, H.; Gong, H. Org. Lett. 2011, 13, 2138.
  (c) Liang, Z.; Xue, W.; Lin, K.; Gong, H. Org. Lett. 2014, 16, 5620.
  (d) Zhang, G.; Xie, Y.; Wang, Z.; Liu, Y.; Huang, H. Chem. Commun. 2015, 51, 1850.
  (e) Ke, M.; Song, Q. J. Org. Chem. 2016, 81, 3654.
  (f) Doi, R.; Ohashi, M.; Ogoshi, S. Angew. Chem., Int. Ed. 2016, 55, 341.
  (g) Ke, M.; Song, Q. Chem. Commun. 2017, 53, 2222.
  (h) Chen, Z.; Wang, X. Org. Biomol. Chem. 2017, 15, 5790.
  (i) Ke, M.; Song, Q. Adv. Synth. Catal. 2017, 359, 384.
  (j) Lu, X.; Wang, Y.; Zhang, B.; Pi, J.; Wang, X.; Gong, T.; Xiao, B.; Fu, Y. J. Am. Chem. Soc. 2017, 139, 12632.
  (k) Kuang, Z.; Li, B.; Song, Q. Chem. Commun. 2018, 54, 34.
17. [17]
  (a) Ojha, D. P.; Gadde, K.; Prabhu, K. R. Org. Lett. 2016, 18, 5062.
  (b) Ding, W.; Song, Q. Org. Chem. Front. 2016, 3, 14.
  (c) Wang, Q.; Yang, J.; Fang, D.; Ren, J.; Dong, B.; Zhou, B.; Zeng, B. Tetrahedron Lett. 2016, 57, 2587.
18. [18]
  (a) Laitar, D. S.; Müller, P.; Sadighi, J. P. J. Am. Chem. Soc. 2005, 127, 17196.
  (b) Bae, S.; Lakshman, M. K. J. Org. Chem. 2008, 73, 1311.
  (c) Kokatla, H. P.; Thomson, P. F.; Bae, S.; Doddi, V. R.; Lakshman, M. K. J. Org. Chem. 2011, 76, 7842.
  (d) Xuan, Q.; Zhao, C.; Song, Q. Org. Biomol. Chem. 2017, 15, 5140.
19. [19]
  (a) Lu, H.; Geng, Z.; Li, J.; Zou, D.; Wu, Y. S.; W, Y. J. Org. Lett. 2016, 18, 2774.
  (b) Yang, K.; Zhou, F.; Kuang, Z.; Gao, G.; Driver, T. Org. Lett. 2016, 18, 4088.
20. [20]
  Enthaler, S. Catal. Lett. 2012, 142, 1306. doi: 10.1007/s10562-012-0897-y
21. [21]
  Xuan, Q.; Song Q. Org. Lett. 2016, 18, 4250. doi: 10.1021/acs.orglett.6b01999
22. [22]
  (a) Lu, H.; Wang, S.; Li, J.; Zou, D.; Wu, Y. S.; Wu, Y. J. Tetrahedron Lett. 2017, 58, 839.
  (b) Zhi, W.; Li, J.; Zou, D.; Wu, Y.; Wu, Y. J. Org. Chem. 2017, 82, 12286.
  (c) Ren, X.; Han, S.; Gao, X.; Li, J.; Zou, D.; Wu, Y.; Wu, Y. Tetrahedron Lett. 2018, 59, 1065.
  (d) Zhi, W.; Li, J.; Zou, D.; Wu, Y.; Wu, Y. Tetrahedron Lett. 2018, 59, 537.
  (e) Zhi, W.; Li, J.; Zou, D.; Wu, Y.; Wu, Y. Tetrahedron Lett. 2018, 59, 2736.
23. [23]
  (a) Geng, Z.; Zhang, Y.; Zheng, L.; Li, J.; Zou, D.; Wu, Y. J.; Wu, Y. S. Tetrahedron Lett. 2016, 57, 3063.
  (b) Zhang, Y.; Geng, Z.; Li, J.; Zou, D.; Wu, Y.; Wu, Y. Adv. Synth. Catal. 2017, 359, 390.
  (c) Zhu, M.; Qiu, Z.; Zhang, Y.; Du, H.; Li, J.; Zou, D.; Wu, Y.; Wu, Y. Tetrahedron Lett. 2017, 58, 2255.
  (d) Zhu, M.; Du, H.; Li, J.; Zou, D.; Wu, Y.; Wu, Y. Tetrahedron Lett. 2018, 59, 1352.
24. [24]
  (a) Menet, C. J. M.; Blanc, J.; Hodges, A. J.; Burli, R. W.; Breccia, P.; Blackaby, W. P.; Van Rompaey, L. J. C.; Fletcher, S. R. WO 2010/010184, 2010.
  (b) Liu, B.; Huang, J.; Zheng, C.; Zhang, Y.; Ouyang, L.; Mao, H.; Nie, B.; Xu, J.; Chen, H. CN 2015/10402418, 2015.
25. [25]
  Chen, Y.; Liu, S.; Cui, P.; Zhang, J.; Liu, Q.; Zhou, H. Tetrahedron Lett. 2019, 60, 327. doi: 10.1016/j.tetlet.2018.12.041
26. [26]
  Christopher, M. V.; Liliya, G. N.; David, W. N.; Heather, A. S.; Andreas, D.; Mark, O. B.; Felix, J. B.; Stephen, A. W. Can. J. Chem. 2001, 79, 1115. doi: 10.1139/v01-090
27. [27]
  Wheaton, S. L.; Humanayun Kabir, S. M.; Zhang, H.; Vogels1, C. M.; Decken, A.; Westcott, S. Cent. Eur. J. Chem. 2010, 8, 725.
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One-Pot, Two-Step Reductive Amination of Boronate Ester Containing Aromatic Amines and Aldehydes Using B2pin2 as Reductant

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One-Pot, Two-Step Reductive Amination of Boronate Ester Containing Aromatic Amines and Aldehydes Using B₂pin₂ as Reductant