Citation: Zhi-Peng Bao, Hefei Yang, Ru-Han A, Yuanrui Wang, Xiao-Feng Wu. Carbonylative five-component synthesis of amides and esters with α-quaternary carbon center[J]. Chinese Chemical Letters, ;2025, 36(11): 111150. doi: 10.1016/j.cclet.2025.111150 shu

Carbonylative five-component synthesis of amides and esters with α-quaternary carbon center

Zhi-Peng Bao ^{a, b} ,
Hefei Yang ^{a, b} ,
Ru-Han A ^{a, b} ,
Yuanrui Wang ^a ,
Xiao-Feng Wu ^{a, b, *,}

a.
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
b.
Leibniz-Institut für Katalyse e.V., Albert-Einstein-Straβe 29a, 18059 Rostock, Germany

xwu2020@dicp.ac.cn

Received Date: 13 January 2025
Revised Date: 13 March 2025
Accepted Date: 26 March 2025
Available Online: 30 March 2025

Figures(4)

Carboxylic acid derivatives with α-quaternary carbon center are one of the most ubiquitous moieties in synthetic and medicinal chemistry. Hence, novel and efficient synthetic methods towards carboxylic acid derivatives with α-quaternary carbon remain in high demand. However, most of the precursors of these complex compounds are not easy to prepare. Reported herein is a carbonylative five-component synthesis of amides and esters with α-quaternary carbon center enabled by palladium catalysis from abundant acrylonitrile, carbon monoxide, fluoroalkyl halides, and nucleophiles. Diverse amides and esters with α-quaternary carbon which contain difluoromethyl or perfluoroalkyl moiety were prepared in good to excellent yields, providing an efficient synthetic platform for sequential transformations.
- Carbonylation,
- Palladium catalyst,
- Amide,
- Alkene,
- Multi component reaction
1. [1]
  X.C. Gan, B. Zhang, N. Dao, et al., Science 384 (2024) 113–118. doi: 10.1126/science.adn5619
2. [2]
  Z. Wang, H. Yin, G.C. Fu, Nature 563 (2018) 379–383. doi: 10.1038/s41586-018-0669-y
3. [3]
  W. Xue, X. Jia, X. Wang, et al., Chem. Soc. Rev. 50 (2021) 4162–4184. doi: 10.1039/d0cs01107j
4. [4]
  J.J. Murphy, D. Bastida, S. Paria, M. Fagnoni, P. Melchiorre, Nature 532 (2016) 218–222. doi: 10.1038/nature17438
5. [5]
  W. Liu, M.N. Lavagnino, C.A. Gould, J. Alcázar, D.W.C. MacMillan, Science 374 (2021) 1258–1263. doi: 10.1126/science.abl4322
6. [6]
  P. Xu, F. Zhou, L. Zhu, J. Zhou, Nature Synth. 2 (2023) 1020–1036. doi: 10.1038/s44160-023-00406-3
7. [7]
  M. Shimizu, Angew. Chem. Int. Ed. 50 (2011) 5998–6000. doi: 10.1002/anie.201101720
8. [8]
  T.G. Chen, H. Zhang, P.K. Mykhailiuk, et al., Angew. Chem. Int. Ed. 58 (2019) 2454–2458. doi: 10.1002/anie.201814524
9. [9]
  R. Jana, T.P. Pathak, M.S. Sigman, Chem. Rev. 111 (2011) 1417–1492. doi: 10.1021/cr100327p
10. [10]
  J. Choi, G.C. Fu, Science 356 (2017) eaaf7230. doi: 10.1126/science.aaf7230
11. [11]
  E.L. Lucas, E.R. Jarvo, Nat. Rev. Chem. 1 (2017) 0065. doi: 10.1038/s41570-017-0065
12. [12]
  G.C. Fu, ACS Cent. Sci. 3 (2017) 692–700. doi: 10.1021/acscentsci.7b00212
13. [13]
  S.L. Zultanski, G.C. Fu, J. Am. Chem. Soc. 135 (2013) 624–627. doi: 10.1021/ja311669p
14. [14]
  X. Wang, G. Ma, Y. Peng, et al., J. Am. Chem. Soc. 140 (2018) 14490–14497. doi: 10.1021/jacs.8b09473
15. [15]
  X. Wang, S. Wang, W. Xue, H. Gong, J. Am. Chem. Soc. 137 (2015) 11562–11565. doi: 10.1021/jacs.5b06255
16. [16]
  Y. Ye, H. Chen, J.L. Sessler, H. Gong, J. Am. Chem. Soc. 141 (2019) 820–824. doi: 10.1021/jacs.8b12801
17. [17]
  H. Chen, X. Jia, Y. Yu, Q. Qian, H. Gong, Angew. Chem. Int. Ed. 56 (2017) 13103–13106. doi: 10.1002/anie.201705521
18. [18]
  X. Lu, Y. Wang, B. Zhang, et al., J. Am. Chem. Soc. 139 (2017) 12632–12637. doi: 10.1021/jacs.7b06469
19. [19]
  L.J. Cheng, S.M. Islam, N.P. Mankad, J. Am. Chem. Soc. 140 (2018) 1159–1164. doi: 10.1021/jacs.7b12582
20. [20]
  Z.T. Ariki, Y. Maekawa, M. Nambo, C.M. Crudden, J. Am. Chem. Soc. 140 (2018) 78–81. doi: 10.1021/jacs.7b10855
21. [21]
  A.L. Pace, F. Xu, W. Liu, M.N. Lavagnino, D.W.C. MacMillan, J. Am. Chem. Soc. 146 (2024) 32925–32932. doi: 10.1021/jacs.4c14942
22. [22]
  D.N. Primer, G.A. Molander, J. Am. Chem. Soc. 139 (2017) 9847–9850. doi: 10.1021/jacs.7b06288
23. [23]
  C. Lohre, T. Dröge, C. Wang, F. Glorius, Chem. Eur. J. 17 (2011) 6052–6055. doi: 10.1002/chem.201100909
24. [24]
  A. Joshi-Pangu, C.Y. Wang, M.R. Biscoe, J. Am. Chem. Soc. 133 (2011) 8478–8481. doi: 10.1021/ja202769t
25. [25]
  P. Ren, L.A. Stern, X. Hu, Angew. Chem. Int. Ed. 51 (2012) 9110–9113. doi: 10.1002/anie.201204275
26. [26]
  T. Iwasaki, H. Takagawa, S.P. Singh, H. Kuniyasu, N. Kambe, J. Am. Chem. Soc. 135 (2013) 9604–9607. doi: 10.1021/ja404285b
27. [27]
  B. Breit, P. Demel, D. Grauer, C. Studte, Chem. Asian J. 1 (2006) 586–597. doi: 10.1002/asia.200600100
28. [28]
  S.A. Green, S. Vásquez-Céspedes, R.A. Shenvi, J. Am. Chem. Soc. 140 (2018) 11317–11324. doi: 10.1021/jacs.8b05868
29. [29]
  S.A. Green, S.W.M. Crossley, J.L.M. Matos, et al., Acc. Chem. Res. 51 (2018) 2628–2640. doi: 10.1021/acs.accounts.8b00337
30. [30]
  T.H. Figueiredo, V. Aroniadou-Anderjaska, F. Qashu, et al., Br. J. Pharmacol. 164 (2011) 1495–1505. doi: 10.1111/j.1476-5381.2011.01427.x
31. [31]
  D.M. Black, D. Bentley, S. Chapel, et al., Clin. Pharmacokinet. 57 (2018) 1359–1367. doi: 10.1007/s40262-018-0656-3
32. [32]
  L. Hillebrands, M. Lamshoeft, A. Lagojda, A. Stork, O. Kayser, J. Agric. Food Chem. 68 (2020) 14123–14134. doi: 10.1021/acs.jafc.0c05277
33. [33]
  R.J. Vaz, J. Kang, Y. Luo, D. Rampe, Bioorg. Med. Chem. Lett. 28 (2018) 446–451. doi: 10.1016/j.bmcl.2017.12.020
34. [34]
  L. Viejo, M. Rubio-Alarcón, R.L. Arribas, et al., Molecules 16 (2022) 4473.
35. [35]
  S.M. Wang, C. Zhao, X. Zhang, H.L. Qin, Org. Biomol. Chem. 17 (2019) 4087–4101. doi: 10.1039/c9ob00699k
36. [36]
  Y. Liu, G.H. Xue, Z. He, et al., J. Am. Chem. Soc. 146 (2024) 28350–28359.
37. [37]
  J.L. Li, S.S. Zhang, L.L. Jiang, et al., Angew. Chem. Int. Ed. 63 (2024) e202420852.
38. [38]
  Q. Zhang, X.Y. Liu, Y.D. Zhang, et al., J. Am. Chem. Soc. 146 (2024) 5051–5055. doi: 10.1021/jacs.3c14032
39. [39]
  H.J. Ai, B.N. Leidecker, P. Dam, et al., Angew. Chem. Int. Ed. 61 (2022) e202211939. doi: 10.1002/anie.202211939
40. [40]
  H.J. Ai, F. Zhao, X.F. Wu, Chin. J. Catal. 47 (2023) 121–128. doi: 10.1016/S1872-2067(22)64208-6
41. [41]
  G. Meng, L. Hu, M. Tomanik, J.Q. Yu, Angew. Chem. Int. Ed. 62 (2023) e202214459. doi: 10.1002/anie.202214459
42. [42]
  X. Ma, J. Albertsma, D. Gabriels, et al., Chem. Soc. Rev. 52 (2023) 3741–3777. doi: 10.1039/d3cs00147d
43. [43]
  H.Y. Yang, Y.H. Yao, M. Chen, Z.H. Ren, Z.H. Guan, J. Am. Chem. Soc. 143 (2021) 7298–7305. doi: 10.1021/jacs.1c03454
44. [44]
  Z.P. Bao, X.F. Wu, Angew. Chem. Int. Ed. 62 (2023) e202301671. doi: 10.1002/anie.202301671
45. [45]
  S. Alazet, M.S. West, P. Patel, S.A.L. Rousseaux, Angew. Chem. Int. Ed. 58 (2019) 10300–10304. doi: 10.1002/anie.201903215
46. [46]
  J. Long, R. Yu, J. Gao, X. Fang, Angew. Chem. Int. Ed. 59 (2020) 6785–6789. doi: 10.1002/anie.202000704
47. [47]
  E.M. Karp, T.R. Eaton, V.S. Nogué, et al., Science 358 (2017) 1307–1310. doi: 10.1126/science.aan1059
48. [48]
  N. Rao, Y.Z. Li, Y.C. Luo, Y. Zhang, X. Zhang, ACS Catal. 13 (2023) 4111–4119. doi: 10.1021/acscatal.2c06149
49. [49]
  Z.P. Bao, Y. Zhang, L.C. Wang, X.F. Wu, Sci. China Chem. 66 (2023) 139–146. doi: 10.1007/s11426-022-1439-1
50. [50]
  Y. Ding, H. Huang, Chem. Catal. 2 (2022) 1467–1479.
51. [51]
  J.X. Xu, C.S. Kuai, B. Chen, X.F. Wu, Chem. Catal. 2 (2022) 477–498.
52. [52]
  Z.P. Bao, Y. Zhang, X.F. Wu, Chem. Sci. 13 (2022) 9387–9391. doi: 10.1039/d2sc02665a
53. [53]
  M. Chen, X. Wang, P. Yang, et al., Angew. Chem. Int. Ed. 59 (2020) 12199–12205. doi: 10.1002/anie.202003288
54. [54]
  S. Cai, Z. Zhao, G. Yang, H. Huang, Nat. Chem. 16 (2024) 1972–1981. doi: 10.1038/s41557-024-01673-z
55. [55]
  Y. Ding, J. Wu, H. Huang, J. Am. Chem. Soc. 145 (2023) 4982–4988. doi: 10.1021/jacs.3c00004
56. [56]
  Y. Ding, J. Wu, T. Zhang, H. Liu, H. Huang, J. Am. Chem. Soc. 146 (2024) 19635–19642. doi: 10.1021/jacs.4c05360
57. [57]
  J. Han, B. Xiao, T.Y. Sun, et al., J. Am. Chem. Soc. 144 (2022) 21800–21807. doi: 10.1021/jacs.2c10559
58. [58]
  H. Hu, F. Teng, J. Liu, et al., Angew. Chem. Int. Ed. 58 (2019) 9225–9229. doi: 10.1002/anie.201904838
59. [59]
  Z. Nie, K. Wu, X. Zhan, et al., Nat. Commun. 15 (2024) 8510. doi: 10.1038/s41467-024-52392-5
60. [60]
  S. Chen, Y.N. Wang, J. Xie, et al., Nat. Commun. 15 (2024) 5479. doi: 10.1038/s41467-024-49870-1
61. [61]
  X. Zhao, X. Feng, F. Chen, et al., Angew. Chem. In. Ed. 60 (2021) 26511–26517. doi: 10.1002/anie.202111061
62. [62]
  X. Zhao, H.Y. Tu, L. Guo, et al., Nat. Commun. 9 (2018) 3488. doi: 10.1038/s41467-018-05951-6
63. [63]
  Y. Zhang, H.Q. Geng, X.F. Wu, Angew. Chem. Int. Ed. 60 (2021) 24292–24298. doi: 10.1002/anie.202111206
64. [64]
  F.P. Wu, Y. Yuan, X.F. Wu, Angew. Chem. Int. Ed. 60 (2021) 25787–25792. doi: 10.1002/anie.202112609
65. [65]
  C.S. Kuai, B.H. Teng, X.F. Wu, Angew. Chem. Int. Ed. 63 (2024) e202318257. doi: 10.1002/anie.202318257
66. [66]
  Y. Wang, H. Yang, Y. Zheng, et al., Nat. Catal. 7 (2024) 1065–1075. doi: 10.1038/s41929-024-01204-6
67. [67]
  B. Lu, F.S. Bao, Z.W. He, W.J. Xiao, J.R. Chen, Chin. J. Chem. 42 (2024) 990–996. doi: 10.1002/cjoc.202300733
68. [68]
  Z.P. Bao, Y. Zhang, X.F. Wu, J. Catal. 413 (2022) 163–167. doi: 10.1016/j.jcat.2022.06.032
69. [69]
  M. Yang, Y. Liu, X. Qi, Y. Zhao, X.F. Wu, Green Synth. Catal. 5 (2024) 211–269.
70. [70]
  Y. Ning, T. Ohwada, F.E. Chen, Green Synth. Catal. 2 (2021) 247–266.
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20. [20]
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