Citation: Chen Diao, Xu Ming-Hua. Transition Metal-Catalyzed Asymmetric Addition of Organoboron Reagents to Imines[J]. Chinese Journal of Organic Chemistry, ;2017, 37(7): 1589-1612. doi: 10.6023/cjoc201704017 shu

Transition Metal-Catalyzed Asymmetric Addition of Organoboron Reagents to Imines

Chen Diao ,
Xu Ming-Hua ^,

State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai 201203

Corresponding author: Xu Ming-Hua, xumh@simm.ac.cn
Received Date: 12 April 2017
Revised Date: 2 May 2017
Available Online: 10 July 2017
Fund Project: the National Natural Science Foundation of China 21472205the National Natural Science Foundation of China 21325209the Program of Shanghai Academic Research Leaders 14XD1404400Project supported by the National Natural Science Foundation of China (Nos. 21325209, 21472205) and the Program of Shanghai Academic Research Leaders (No. 14XD1404400)

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Chiral amines are important building blocks in organic synthesis, they also present in numerous natural products, biologically active compounds and pharmaceutical agents. In recent years, the use of various organoboron reagents in transition metal-catalyzed reactions has attracted considerable attentions because of their ready avilibility, low toxicity, good air and moisture stability as well as high functional group compatibility. This review summarizes the remarkable progress and advances in transition metal-catalyzed asymmetric addition of organoboron reagents to imines over the past few years, providing an overview of the recent achievements in stereoselective synthesis of α-chiral amines by using chiral auxiliary or chiral catalysis strategies. At the present time, rhodium-based asymmetric catalysis has proven to be the most efficient and reliable approach to furnish highly optically active α-chiral amines. Varieties of chiral ligands including monophosphines, biphosphines, amidomonophosphanes, phosphoramidites, phosphites, dienes, sulfur-olefins, phosphorus-olefins have showed the great potential in many asymmetric additions of organoboron reagents to imines, enabling the access of both secondary and tertiary α-chiral amines with good to excellent enantioselectivities. On the other hand, important progress has been made in developing effective palladium catalysts mainly based on chiral pyridine-oxazoline and phosphine-oxazoline ligands. However, future studies in this area towards the objective of developing more efficient, practical and general methods remain challenging.
- asymmetric synthesis,
- chiral amine,
- metal catalysis,
- asymmetric addition,
- organoboron
1. [1]
  (a) Calderon, S. N.; Rothman, R. B.; Porreca, F.; Flippen-Anderson, J. L.; McNutt, R. W.; Xu, H.; Smith, L. E.; Bilsky, E. J.; Davis, P.; Rice, K. C. J. Med. Chem. 1994, 37, 2125.
  (b) Van Bambeke, F.; Van Laethem, Y.; Courvalin, P.; Tulkens, P. M. Drugs 2004, 64, 913.
  (c) Calderon, S. N.; Rice, K. C.; Rothman, R. B.; Porreca, F.; Anderson, J. L. F.; Kayakiri, H.; Xu, H.; Becketts, K.; Smith, L. E.; Bilsky, E. J.; Davis, P.; Horvath, R. J. Med. Chem. 1997, 40, 695.
  (d) Wiseman, L. R.; Benfield, P. Drugs 1993, 2, 295.
2. [2]
  (a) Deng, Q. H.; Xu, H. W.; Yuen, A. W.; Xu, Z. J.; Che, C. M. Org. Lett. 2008, 10, 1529.
  (b) Lee, E. C.; Fu, G. C. J. Am. Chem. Soc. 2007, 129, 12066.
  (c) Xu, B.; Zhu, S. F.; Zuo, X. D.; Zhang, Z. C.; Zhou, Q. L. Angew. Chem., Int. Ed. 2014, 53, 3913.
  (d) Xu, B.; Zhu, S. F.; Xie, X. L.; Shen, J. J.; Zhou, Q. L. Angew. Chem., Int. Ed. 2011, 50, 11483.
3. [3]
  (a) Tang, W.; Zhang, X. Chem. Rev. 2003, 103, 3029.
  (b) Kobayashi, S.; Ishitani, H. Chem. Rev. 1999, 99, 1069.
  (c) Wang, D. S.; Chen, Q. A.; Lu, S. M.; Zhou, Y. G. Chem. Rev. 2012, 112, 2557.
4. [4]
  (a) Wang, J.; Liu, X.; Feng, X. Chem. Rev. 2011, 111, 6947.
  (b) Kobayashi, S.; Mori, Y.; Fossey, J. S.; Salter, M. M. Chem. Rev. 2011, 111, 2626.
  (c) Marques, C. S.; Burke, A. J. ChemCatChem 2011, 3, 635.
  (d) Robak, M. T.; Herbage, M. A.; Ellman, J. A. Chem. Rev. 2010, 110, 3600.
  (e) Lin, G.-Q.; Xu, M.-H.; Zhong, Y.-W.; Sun, X.-W. Acc. Chem. Res. 2008, 41, 831.
  (f) Ellman, J. A.; Owens, T. D.; Tang, T. P. Acc. Chem. Res. 2002, 35, 984.
5. [5]
6. [6]
  Weix, D. J.; Shi, Y.; Ellman, J. A. J. Am. Chem. Soc. 2005, 127, 1092. doi: 10.1021/ja044003d
7. [7]
  Bolshan, Y.; Batey, R. A. Org. Lett. 2005, 7, 1481. doi: 10.1021/ol050014f
8. [8]
  Beenen, M. A.; Weix, D. J.; Ellman, J. A. J. Am. Chem. Soc. 2006, 128, 6304. doi: 10.1021/ja060529h
9. [9]
  Brak, K.; Ellman, J. A. J. Am. Chem. Soc. 2009, 131, 3850. doi: 10.1021/ja9002603
10. [10]
  Brak, K.; Ellman, J. A. J. Org. Chem. 2010, 75, 3147. doi: 10.1021/jo100318s
11. [11]
  Brak, K.; Ellman, J. A. Org. Lett. 2010, 12, 2004. doi: 10.1021/ol100470g
12. [12]
  Dai, H.; Lu, X. Org. Lett. 2007, 9, 3077. doi: 10.1021/ol0711220
13. [13]
  Kuriyama, M.; Soeta, T.; Hao, X.; Chen, Q.; Tomioka, K. J. Am. Chem. Soc. 2004, 126, 8128. doi: 10.1021/ja0475398
14. [14]
  Hao, X.; Kuriyama, M.; Chen, Q.; Yamamoto, Y.; Yamada, K.; Tomioka, K. Org. Lett. 2009, 11, 4470. doi: 10.1021/ol901866y
15. [15]
  Hao, X.; Chen, Q.; Yamada, K.-i.; Yamamoto, Y.; Tomioka, K. Tetrahedron 2011, 67, 6469. doi: 10.1016/j.tet.2011.06.033
16. [16]
  Hao, X.; Chen, Q.; Kuriyama, M.; Yamada, K.-I.; Yamamoto, Y.; Tomioka, K. Cat. Sci. Tec. 2011, 1, 62. doi: 10.1039/c0cy00083c
17. [17]
  Trincado, M.; Ellman, J. A. Angew. Chem., Int. Ed. 2008, 47, 5623. doi: 10.1002/anie.v47:30
18. [18]
  Jagt, R. B.; Toullec, P. Y.; Geerdink, D.; de Vries, J. G.; Feringa, B. L.; Minnaard, A. J. Angew. Chem., Int. Ed. 2006, 45, 2789. doi: 10.1002/(ISSN)1521-3773
19. [19]
  Duan, H.-F.; Jia, Y.-X.; Wang, L.-X.; Zhou, Q.-L. Org. Lett. 2006, 8, 2567. doi: 10.1021/ol060755w
20. [20]
  Kurihara, K.; Yamamoto, Y.; Miyaura, N. Adv. Synth. Catal. 2009, 351, 260. doi: 10.1002/adsc.200800631
21. [21]
  Lee, A.; Kim, H. J. Org. Chem. 2016, 81, 3520. doi: 10.1021/acs.joc.6b00033
22. [22]
  Tokunaga, N.; Otomaru, Y.; Okamoto, K.; Ueyama, K.; Shintani, R.; Hayashi, T. J. Am. Chem. Soc. 2004, 126, 13584. doi: 10.1021/ja044790e
23. [23]
  Otomaru, Y.; Kina, A.; Shintani, R.; Hayashi, T. Tetrahedron:Asymmetry 2005, 16, 1673. doi: 10.1016/j.tetasy.2005.02.022
24. [24]
  Okamoto, K.; Hayashi, T.; Rawal, V. H. Chem. Commun. 2009, 4815.
25. [25]
  Crampton, R.; Woodward, S.; Fox, M. Adv. Synth. Catal. 2011, 353, 903. doi: 10.1002/adsc.v353.6
26. [26]
  Crampton, R. H.; Fox, M.; Woodward, S. Tetrahedron:Asymmetry 2013, 24, 599. doi: 10.1016/j.tetasy.2013.04.006
27. [27]
  Fujioka, M.; Morimoto, T.; Tsumagari, T.; Tanimoto, H.; Nishiyama, Y.; Kakiuchi, K. J. Org. Chem. 2012, 77, 2911. doi: 10.1021/jo300201g
28. [28]
  Wang, Z.-Q.; Feng, C.-G.; Xu, M.-H.; Lin, G.-Q. J. Am. Chem. Soc. 2007, 129, 5336. doi: 10.1021/ja0710914
29. [29]
  Wang, Z.-Q.; Feng, C.-G.; Zhang, S.-S.; Xu, M.-H.; Lin, G.-Q. Angew. Chem., Int. Ed. 2010, 49, 5780. doi: 10.1002/anie.v49:33
30. [30]
  Wang, L.; Wang, Z.-Q.; Xu, M.-H.; Lin, G.-Q. Synthesis 2010, 3263.
31. [31]
  Yang, H.-Y.; Xu, M.-H. Chem. Commun. 2010, 46, 9223. doi: 10.1039/c0cc04086j
32. [32]
  Shao, C.; Yu, H.-J.; Wu, N.-Y.; Feng, C.-G.; Lin, G.-Q. Org. Lett. 2010, 12, 3820. doi: 10.1021/ol101531r
33. [33]
  Cui, Z.; Yu, H.-J.; Yang, R.-F.; Gao, W.-Y.; Feng, C.-G.; Lin, G.-Q. J. Am. Chem. Soc. 2011, 133, 12394. doi: 10.1021/ja2046217
34. [34]
  Cao, Z.; Du, H. Org. Lett. 2010, 12, 2602. doi: 10.1021/ol1008087
35. [35]
  Chen, C.-C.; Gopula, B.; Syu, J.-F.; Pan, J.-H.; Kuo, T.-S.; Wu, P.-Y.; Henschke, J. P.; Wu, H.-L. J. Org. Chem. 2014, 79, 8077. doi: 10.1021/jo5012653
36. [36]
  Luo, Y.; Carnell, A. J.; Lam, H. W. Angew. Chem., Int. Ed. 2012, 51, 6762. doi: 10.1002/anie.201202136
37. [37]
  Luo, Y.; Hepburn, H. B.; Chotsaeng, N.; Lam, H. W. Angew. Chem., Int. Ed. 2012, 51, 8309. doi: 10.1002/anie.v51.33
38. [38]
  Cui, Z.; Chen, Y.-J.; Gao, W.-Y.; Feng, C.-G.; Lin, G.-Q. Org. Lett. 2014, 16, 1016. doi: 10.1021/ol5000154
39. [39]
  Gopula, B.; Chiang, C. W.; Lee, W. Z.; Kuo, T. S.; Wu, P. Y.; Henschke, J. P.; Wu, H. L. Org. Lett. 2014, 16, 632. doi: 10.1021/ol4035897
40. [40]
  Shintani, R.; Narui, R.; Tsutsumi, Y.; Hayashi, S.; Hayashi, T. Chem. Commun. 2011, 47, 6123. doi: 10.1039/c1cc11823d
41. [41]
  Wang, H.; Xu, M.-H. Synthesis 2013, 45, 2125. doi: 10.1055/s-00000084
42. [42]
  Jiang, T.; Chen, W.-W.; Xu, M.-H. Org. Lett. 2017, 19, 2138. doi: 10.1021/acs.orglett.7b00776
43. [43]
  Chen, J.; Lu, X.; Lou, W.; Ye, Y.; Jiang, H.; Zeng, W. J. Org. Chem. 2012, 77, 8541. doi: 10.1021/jo301423e
44. [44]
  Jung, H. H.; Buesking, A. W.; Ellman, J. A. Org. Lett. 2011, 13, 3912. doi: 10.1021/ol201438k
45. [45]
  Wada, R.; Shibuguchi, T.; Makino, S.; Oisaki, K.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2006, 128, 7687. doi: 10.1021/ja061510h
46. [46]
  Osborne, C. A.; Endean, T. B. D.; Jarvo, E. R. Org. Lett. 2015, 17, 5340. doi: 10.1021/acs.orglett.5b02692
47. [47]
  Kong, J.; McLaughlin, M.; Belyk, K.; Mondschein, R. Org. Lett. 2015, 17, 5520. doi: 10.1021/acs.orglett.5b02032
48. [48]
  Shintani, R.; Takeda, M.; Tsuji, T.; Hayashi, T. J. Am. Chem. Soc. 2010, 132, 13168. doi: 10.1021/ja106114q
49. [49]
  Shintani, R.; Takeda, M.; Soh, Y. T.; Ito, T.; Hayashi, T. Org. Lett. 2011, 13, 2977. doi: 10.1021/ol200958q
50. [50]
  Nishimura, T.; Noishiki, A.; Tsui, G. C.; Hayashi, T. J. Am. Chem. Soc. 2012, 134, 5056. doi: 10.1021/ja300697c
51. [51]
  Wang, H.; Jiang, T.; Xu, M.-H. J. Am. Chem. Soc. 2013, 135, 971. doi: 10.1021/ja3110818
52. [52]
  Wang, H.; Li, Y.; Xu, M.-H. Org. Lett. 2014, 16, 3962. doi: 10.1021/ol501770q
53. [53]
  Jiang, T.; Wang, Z.; Xu, M.-H. Org. Lett. 2015, 17, 528. doi: 10.1021/ol503537w
54. [54]
  Zhang, X.; Xu, B.; Xu, M.-H. Org. Chem. Front. 2016, 3, 944. doi: 10.1039/C6QO00191B
55. [55]
  Li, Y.; Yu, Y.-N.; Xu, M.-H. ACS Catal. 2016, 6, 661. doi: 10.1021/acscatal.5b02403
56. [56]
  Zhang, Y.-F.; Chen, D.; Chen, W.-W.; Xu, M.-H. Org. Lett. 2016, 18, 2726. doi: 10.1021/acs.orglett.6b01183
57. [57]
  Nishimura, T.; Noishiki, A.; Ebe, Y.; Hayashi, T. Angew. Chem., Int. Ed. 2013, 52, 1777. doi: 10.1002/anie.v52.6
58. [58]
  Nishimura, T.; Ebe, Y.; Fujimoto, H.; Hayashi, T. Chem. Commun. 2013, 49, 5504. doi: 10.1039/c3cc42071j
59. [59]
  Chen, Y.-J.; Chen, Y.-H.; Feng, C.-G.; Lin, G.-Q. Org. Lett. 2014, 16, 3400. doi: 10.1021/ol501464e
60. [60]
  Takechi, R.; Nishimura, T. Org. Biomol. Chem. 2015, 13, 4918. doi: 10.1039/C5OB00431D
61. [61]
  Yang, G.; Zhang, W. Angew. Chem., Int. Ed. 2013, 52, 7540. doi: 10.1002/anie.201302861
62. [62]
  Jiang, C.; Lu, Y.; Hayashi, T. Angew. Chem., Int. Ed. 2014, 53, 9936. doi: 10.1002/anie.201406147
63. [63]
  Quan, M.; Yang, G.; Xie, F.; Gridnev, I. D.; Zhang, W. Org. Chem. Front. 2015, 2, 398. doi: 10.1039/C4QO00347K
64. [64]
  Álvarez-Casao, Y.; Monge, D.; Álvarez, E.; Álvarez, E.; Fernández, Lassaletta, J. M. Org. Lett. 2015, 17, 5104. doi: 10.1021/acs.orglett.5b02613
65. [65]
  He, Q.; Wu, L.; Kou, X.; Butt, N.; Yang, G.; Zhang, W. Org. Lett. 2016, 18, 288. doi: 10.1021/acs.orglett.5b03458
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