Citation: Chen Si, Zhao Yanchuan. C(sp³)—C(sp³) Bond Formation via Transition-Metal Mediated and Catalyzed Reductive Homocouplings[J]. Chinese Journal of Organic Chemistry, ;2020, 40(10): 3078-3093. doi: 10.6023/cjoc202005072 shu

C(sp³)—C(sp³) Bond Formation via Transition-Metal Mediated and Catalyzed Reductive Homocouplings

Chen Si ^a ,
Zhao Yanchuan ^a,b,,

a.
CAS Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
b.
CAS Key Laboratory of Energy Regulation Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Corresponding author: Zhao Yanchuan, zhaoyanchuan@sioc.ac.cn
Received Date: 26 May 2020
Revised Date: 19 July 2020
Available Online: 30 July 2020
Fund Project: the National Natural Science Foundation of China 21421002Project supported by the National Natural Science Foundation of China (Nos. 21421002, 21871291, 91956120), and the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDC 06020102)the Strategic Priority Research Program of the Chinese Academy of Sciences XDC 06020102the National Natural Science Foundation of China 91956120the National Natural Science Foundation of China 21871291

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C(sp³)-C(sp³) bond coupling is of great significance in organic synthesis, among which reductive homocoupling has showed its special superiority in construction of symmetrical molecular structures. These reactions are usually operationally simple, which utilize organohalides as substrates, avoiding the handling of highly reactive organometallic reagents. The use of non-precise metals as the catalyst makes reductive homocouplings amenable for large-scale synthesis. Improved efficiency and selectivity have been observed in systems involving photoredox catalytic processes, ionic-liquids, and inorganic nanomaterials. This review aims to summarize the development of reductive couplings. In this review, various reductive homocouplings are summarized, where transition metals, such as cobalt, nickel, copper, titanium, and rhodium are involved. Photo-mediated reductive couplings are then highlighted followed by a discussion on applications of reductive couplings in natural products synthesis and polymer sciences.
- C(sp³)-C(sp³) bond formation,
- reductive homocoupling,
- transition-metal catalysis,
- photoredox catalysis,
- total synthesis
1. [1]
  Wu, X. F.; Anbarasan, P.; Neumann, H.; Beller, M. Angew. Chem. Int. Ed. 2010, 49, 9047. doi: 10.1002/anie.201006374
2. [2]
  Li, Z. L.; Jin, J.; Huang, S. H. Chin. J. Org. Chem. 2020, 40, 563(in Chinese).
3. [3]
  Dong, K.; Liu, Q.; Wu, L. Z. Acta Chim. Sinica 2020, 78, 299(in Chinese).
4. [4]
  Li, Y. Q.; Fan, Y. H.; Jia, Q. F. Chin. J. Org. Chem. 2019, 39, 350(in Chinese).
5. [5]
  Liu, L.; Xi, Z. F. Chin. J. Chem. 2019, 36, 1213.
6. [6]
  Wang, K.; Kong, W. Q. Chin. J. Chem. 2018, 36, 247. doi: 10.1002/cjoc.201700745
7. [7]
  Voloshchuk, T.; Farina, N. S.; Wauchope, O. R.; Kiprowska, M.; Haberfield, P.; Greer, A. J. Nat. Prod. 2004, 67, 1141. doi: 10.1021/np049899e
8. [8]
  Buschleb, M.; Dorich, S.; Hanessian, S.; Tao, D.; Schenthal, K. B.; Overman, L. E. Angew. Chem. Int. Ed. 2016, 55, 4156. doi: 10.1002/anie.201507549
9. [9]
  Kirchhoff, J. H.; Dai, C.; Fu, G. C. Angew. Chem. Int. Ed. 2002, 41, 1945. doi: 10.1002/1521-3773(20020603)41:11<1945::AID-ANIE1945>3.0.CO;2-7
10. [10]
  Hua, S. K.; Hu, Q. P.; Ren, J. M. Zeng, B. B. Synthesis 2013, 45, 518. doi: 10.1055/s-0032-1316841
11. [11]
  Tran, U. P. N.; Hock, K. J.; Gordon, C. P.; Koenigs, R. M.; Nguyen, T. V. Chem. Commun. 2017, 53, 4950. doi: 10.1039/C7CC02033C
12. [12]
  Du, F.; Zhou, Q.; Liu, D.; Fang, T.; Shi, Y.; Du, Y.; Chen, G. Synlett 2018, 29, 779. doi: 10.1055/s-0036-1591892
13. [13]
  Yamada, Y.; Momose, D. Chem. Lett. 1981, 10, 1277. doi: 10.1246/cl.1981.1277
14. [14]
  Barhdadi, R.; Courtinard, C.; Nedelec, J. Y.; Troupel, M. Chem. Comm. 2003, 12, 1434.
15. [15]
  Schriver, G. W. Tetrahedron Lett. 1988, 29, 1521. doi: 10.1016/S0040-4039(00)80341-X
16. [16]
  Albrecht, M. Synthesis 1996, 230.
17. [17]
  Shimizu, T.; Tanaka, K.; Paudel, A.; Yamato, T. J. Chem. Res. 2009, 570.
18. [18]
  Gozhina, O. V.; Thomassen, I. K.; Lejon, T. Synth. Commun. 2013, 43, 1867. doi: 10.1080/00397911.2012.675459
19. [19]
  Zhang, W.; Li, A. Nat. Chem. 2017, 9, 198. doi: 10.1038/nchem.2734
20. [20]
  Aresta, M.; Rossi, M.; Sacco, A. Inorg. Chim. Acta 1969, 3, 227; doi: 10.1016/S0020-1693(00)92484-8
21. [21]
  Momose, D.; Iguchi, K.; Sugiyama, T.; Yamada, Y. Chem. Pharm. Bull. 1984, 32, 1840.
22. [22]
  Fallon, B. J.; Corce, V.; Amatore, M.; Aubert, C.; Chemla, F.; Ferreira, F.; Perez-Luna, A.; Petit, M. New J. Chem. 2016, 40, 9912. doi: 10.1039/C6NJ03265F
23. [23]
  Cai, Y.; Qian, X.; Gosmini, C. Adv. Synth. Catal. 2016, 15, 358.
24. [24]
  Giedyk, M.; Goliszewska, K.; Gryko, D. Chem. Soc. Rev. 2015, 44, 3391. doi: 10.1039/C5CS00165J
25. [25]
  Petrovic, Z.; Mojsilovic, B.; Bugarcic, Z. M. J. Mol. Catal. A:Chem. 2001, 170, 267. doi: 10.1016/S1381-1169(00)00557-4
26. [26]
  Shey, J.; McGinley, C. M.; McCauley, K. M.; Dearth, A. S.; Young, B. T.; Donk, W. A. J. Org. Chem. 2002, 67, 837. doi: 10.1021/jo0160470
27. [27]
  Giedyk, M.; Fedosov, S. N.; Gryko, D. Chem. Commun. 2014, 50, 4674.
28. [28]
  Schrauzer, G. N.; Grate, J. H. J. Am. Chem. Soc. 1981, 103, 541. doi: 10.1021/ja00393a009
29. [29]
  Iyoda, M.; Sakaitani, M.; Otsuka, H.; Oda, M. Chem. Lett. 1985, 14, 127. doi: 10.1246/cl.1985.127
30. [30]
  Prinsell, M. R.; Everson, D. A.; Weix, D. J. Chem. Commun. 2010, 46, 5743. doi: 10.1039/c0cc01716g
31. [31]
  Zhou, J.; Fu, G. J. Am. Chem, Soc. 2003. 125. 14726. doi: 10.1021/ja0389366
32. [32]
  Vechorkim, O. Proust, V. Hu, X. J. Am. Chem. Soc. 2009, 131, 9756.
33. [33]
  Chen, T.; Yang, L.; Li, L.; Huang, K. W. Tetrahedron 2012, 68, 6152. doi: 10.1016/j.tet.2012.05.075
34. [34]
  Mboyi, C. D.; Gaillard, S.; Mabaye, M. D.; Pannetier, N.; Renaud, J. L. Tetrahedron 2013, 69, 4875. doi: 10.1016/j.tet.2013.04.073
35. [35]
  Liu, Y. J.; Xiao, S. H.; Qi, Y.; Du, F. Chem. Asian J. 2017, 12, 673. doi: 10.1002/asia.201601712
36. [36]
  Nayak, M. K.; Mukhi, P.; Mohanty, A. Rana, S. S.; Arora, R.; Narjinari, H.; Roy, S. J. Chem. Sci. 2019, 131, 59.
37. [37]
  Liu, Y. J.; Zhang, D. M.; Xiao, S. H.; Qi, Y.; Liu, S. F. Chem. Asian J. 2019, 8, 858.
38. [38]
  Teo, W. J.; Wang, Z.; Xue, F.; Andy Hor, T. S.; Zhao, J. Dalton Trans. 2016, 45, 7312. doi: 10.1039/C6DT00252H
39. [39]
  Komeyama, K.; Tsunemitsu, R.; Michiyuji, T.; Yoshida, H.; Osaka, I. Molecules 2019, 24, 1458.
40. [40]
  Jacobson, R. R.; Tyklar, Z.; Karlin, K. D. Inorg. Chim. Acta 1991, 181, 111.
41. [41]
  Ma, J.; Chan, T. H. Tetrahedron Lett. 1998, 39, 2499. doi: 10.1016/S0040-4039(98)00348-7
42. [42]
  Liu, J.; Li, B. Synth. Commun. 2007, 37, 3273. doi: 10.1080/00397910701483340
43. [43]
  Shekarriz, M.; Adib, M.; Biabani, T.; Taghipoor, S. J. Chem. Res. 2012, 29.
44. [44]
  Hu, Y. L.; Li, F.; Gu, G. L. Catal. Lett. 2011, 141, 467. doi: 10.1007/s10562-010-0535-5
45. [45]
  Sato, K.; Inoue, Y.; Mori, T.; Sakaue, A.; Taruo, A.; Omote, M.; Kumadaki, I.; Ando, A. Org. Lett. 2014, 16, 3756. doi: 10.1021/ol501619w
46. [46]
  Qian, Y.; Li, G.; Huang, Y. Z. J. Organomet. Chem. 1990, 381, 29.
47. [47]
  Barrero, A. F.; Herrador, M. M.; Moral, J. F. Q.; Arteaga, P.; Akssira, M.; Hanbali, F. E.; Artega, J. F.; Dieguez, H. R.; Sanchez, E. M. J. Org. Chem. 2007, 72, 2251.
48. [48]
  Barrero, A. F.; Herrador, M. M.; Moral, J. F. Q.; Arteaga, P.; Arteaga, J. F.; Piedra, M.; Sanchez, E, M, Org. Lett. 2005, 7, 2301. doi: 10.1021/ol050335r
49. [49]
  Gilbert, B. C.; Lindsay, C. I.; McGrail, P. T.; Parsons, A. F.; Whittaker, D. T. E. Synth. Commun. 1999, 29, 2711. doi: 10.1080/00397919908086433
50. [50]
  Huther, N.; McGrail, P. T.; Parsons, A. F. Eur. J. Org. Chem. 2004, 1740.
51. [51]
  Hironaka, K.; Fukuzumi, S.; Tanaka, T. J. Chem. Soc., Perkin Trans. 21984, 1705.
52. [52]
  Kern, J. M.; Sauvage, J. P. J. Chem. Soc., Chem. Commun. 1987, 546.
53. [53]
  Fukuzumi, S.; Ishikawa, K.; Tanaka, T. Organometallics 1987, 6, 358. doi: 10.1021/om00145a020
54. [54]
  Zhang, Y.; Petersen, J. L.; Milsmann, C. Organometallics 2018, 37, 4488.
55. [55]
  Park, G.; Yi, S. Y.; Jung, J.; Cho, E. J.; You. Y. Chem. Eur. J. 2016, 22, 17790. doi: 10.1002/chem.201603517
56. [56]
  Masuda, Y.; Ishida, N.; Murakami, M. Eur. J. Org. Chem. 2016, 5822.
57. [57]
  Lanterna, A. E.; Elhage, A.; Scaiano, J. C. Catal. Sci. Technol. 2015, 5, 4336.
58. [58]
  Vrettou, M.; Gray, A. A.; Brewer, A. R. E.; Barret, A. G. M. Tetrahedron 2007, 63, 1487.
59. [59]
  Gentry, E. C. G.; Rono, L. J.; Hale, M. E.; Matsuura, R.; Knowles, R. R.; J. Am. Chem. Soc. 2018, 140, 3394. doi: 10.1021/jacs.7b13616
60. [60]
  Lathrop, S. P.; Pompeo, M. T.; Chang, W. T. T.; Movassaghi, M. J. Am. Chem. Soc. 2016, 138, 7763. doi: 10.1021/jacs.6b04072
61. [61]
  Ding, M.; Liang, K. J.; Pan, Rui.; Zhang, H. B.; Xia, C. F. J. Org. Chem. 2015, 80, 10309.
62. [62]
  Bagal, S. K.; Adlington, R. M.; Baldwin, J. E.; Marquez. R. J. Org. Chem. 2004, 69, 9100.
63. [63]
  Bagal, S. K.; Adlington, R. M.; Marquez, R.; Cowley, A. R.; Baldwin, J. E. Tetrahedron Lett. 2003, 44, 4993.
64. [64]
  Bagal, S. K.; Adlington, R. M.; Baldwin, J. E.; Marquez, R. Cowley, A. Org. Lett. 2003, 5, 3049. doi: 10.1021/ol035022f
65. [65]
  Movassaghi, M.; Schmidt, M, A. Angew. Chem. Int. Ed. 2007, 46, 3725. doi: 10.1002/anie.200700705
66. [66]
  Iwasa, E.; Hamashima, Y.; Fujishiro, S.; Higuchi, E.; Ito, A.; Yoshida, M.; Sodeoka, M. J. Am. Chem. Soc. 2010, 132, 4078. doi: 10.1021/ja101280p
67. [67]
  Peng, Y.; Luo, L.; Yan, C. S.; Zhang, J. J.; Wang, Y. W. J. Org. Chem. 2013, 78, 10960.
68. [68]
  Wada, M.; Murata, T.; Oikawa, H.; Oguri, H. Org. Biomol. Chem. 2014, 12, 298.
69. [69]
  Goldup, S. M.; Leigh, D. A.; McBurney, R. T.; McGonigal, P. R.; Plant, A. Chem. Sci. 2010, 1, 383.
70. [70]
  Gorham, W. F. J. Poly. Sci. 1966, 4, 3027. doi: 10.1002/pol.1966.150041209
71. [71]
  Liu, Z.; Wang, Q. RSC Adv. 2016, 6, 39568. doi: 10.1039/C6RA02669A
72. [72]
  Liu, Z.; Wang, Q. Polymer 2017, 100, 56.
73. [73]
  Liu, Z.; Wang, Q. ACS Macro Lett. 2018, 7, 604.
74. [74]
  Zhu, R.; Swager, T. M. J. Am. Chem. Soc. 2018. 140. 5211. doi: 10.1021/jacs.8b01106
75. [75]
  Chen, S.; Zhao, Y. Chin. J. Chem. 2020, 38, 953.
76. [76]
  Pike, R. D.; Starnes Jr, W. H.; Jeng, J. P.; Bryant, W. S.; Kourtesis, P.; Adams, C. W.; Bunge, S. D.; Kang, Y. M.; Kim, A. S.; Kim, J. H.; Macko, J. A.; O'Brien, C. P. Macromolecules 1997, 30, 6957. doi: 10.1021/ma9707749
77. [77]
  Gao, B.; Zhao, Y. C.; Ni, C. F.; Hu, J. B. Org. Lett. 2014, 16, 102. doi: 10.1021/ol403083e
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沈阳化工大学材料科学与工程学院沈阳 110142

C(sp3)—C(sp3) Bond Formation via Transition-Metal Mediated and Catalyzed Reductive Homocouplings

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通讯作者: 陈斌, bchen63@163.com

C(sp³)—C(sp³) Bond Formation via Transition-Metal Mediated and Catalyzed Reductive Homocouplings