Citation: Junyou Ding, Xiaotong Li, Hongmin Lin, Bochao Ye, Xing Zhou, Feihu Cui, Yingming Pan, Haitao Tang. Highly regioselective hydrogermylation of unsaturated C-C bonds over ligand-control single atom palladium catalysts[J]. Chinese Chemical Letters, ;2025, 36(11): 111286. doi: 10.1016/j.cclet.2025.111286 shu

Highly regioselective hydrogermylation of unsaturated C-C bonds over ligand-control single atom palladium catalysts

Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources (Ministry of Education of China), Guangxi Key Laboratory of Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004, China

panym@mailbox.gxnu.edu.cn

httang@gxnu.edu.cn

Received Date: 2 January 2025
Revised Date: 6 May 2025
Accepted Date: 7 May 2025
Available Online: 8 May 2025

Figures(9)

The selective addition reaction of unsaturated C–C bonds has always been a classic and constant research topic. Different from well-developed hydroboration, hydrosilylation, and hydrostannylation reaction, hydrogermylation reaction remains challenging which hasn't been much reported. Herein, we developed a new metal-porous ligand polymers Pd₁@POL-PPh_nCy_m (n + m = 3) with monoatomic dispersion characteristics for highly selective and efficient hydrogermylation of unsaturated C–C bonds, including alkynes, alkenes, and allenes. X-ray photoelectron spectroscopy and theoretical calculations further proved the introduction of cyclohexyl could gently adjust the charge on monoatomic Pd center which effectively facilitate the recognition and transformation of various substrates. With the electrically fine-tuned single atom palladium catalysts, we realized the α-germanium addition for the first time, obtaining corresponding allyl germanium and alkyl germanium compounds.
- Hydrogermylation,
- Unsaturated C-C bonds,
- Single atom catalyst,
- Catalyst design,
- Regio- and stereo-selectivity
1. [1]
  X. Zeng, Chem. Rev. 113 (2013) 6864–6900. doi: 10.1021/cr400082n
2. [2]
  W. Ai, R. Zhong, X. Liu, Q. Liu, Chem. Rev. 119 (2018) 2876–2953.
3. [3]
  C. Cheng, J.F. Hartwig, Chem. Rev. 115 (2015) 8946–8975. doi: 10.1021/cr5006414
4. [4]
  C. Li, Z. Yang, L. Wang, et al., Angew. Chem. Int. Ed. 59 (2020) 6278–6283. doi: 10.1002/anie.201915716
5. [5]
  C. Li, S. Song, Y. Li, et al., Nat. Commun. 12 (2021) 3813. doi: 10.1038/s41467-021-24117-5
6. [6]
  J.S. Jia, Y. Cao, T.X. Wu, et al., ACS Catal. 11 (2021) 6944–6950. doi: 10.1021/acscatal.1c01996
7. [7]
  M. Zhong, Y. Gagné, T.O. Hope, et al., Angew. Chem. Int. Ed. 60 (2021) 14498–14503. doi: 10.1002/anie.202101874
8. [8]
  H. Wen, X. Wan, Z. Huang, Angew. Chem. Int. Ed. 57 (2018) 6319–6323. doi: 10.1002/anie.201802806
9. [9]
  L.P. Pang, X.Y. Li, S.C. Ren, et al., Nano Res. 15 (2022) 7091–7098. doi: 10.1007/s12274-022-4395-2
10. [10]
  D. Yang, Q. Yan, E. Zhu, J. Lv, W.M. He, Chin. Chem. Lett. 33 (2022) 1798–1816. doi: 10.1016/j.cclet.2021.09.068
11. [11]
  Z. Cheng, M. Li, X. Zhang, Y. Sun, et al., Angew. Chem. Int. Ed. 62 (2022) e202215029.
12. [12]
  X.M. Chen, L. Song, J. Pan, et al., Chin. Chem. Lett. 35 (2024) 110112. doi: 10.1016/j.cclet.2024.110112
13. [13]
  S. Ren, B. Ye, S. Li, et al., Nano Res. 15 (2021) 1500–1508. doi: 10.1007/978-981-15-8411-4_198
14. [14]
  S.H. Yang, J.C. Song, H. Yang, Chin. Chem. Lett. 34 (2023) 108131. doi: 10.1016/j.cclet.2023.108131
15. [15]
  W.Y. Huang, G.Q. Wang, W.H. Li, et al., Chem 6 (2020) 2300–2313. doi: 10.1016/j.chempr.2020.06.020
16. [16]
  H.C. Li, M. Zhang, Q. Lv, et al., Chin. Chem. Lett. 36 (2025) 110579. doi: 10.1016/j.cclet.2024.110579
17. [17]
  J. Jiang, K.L. Wang, X. Li, et al., Chin. Chem. Lett. 34 (2023) 108699. doi: 10.1016/j.cclet.2023.108699
18. [18]
  C. Fricke, F. Schoenebeck, Acc. Chem. Res. 53 (2020) 2715–2725. doi: 10.1021/acs.accounts.0c00527
19. [19]
  M.R. Radzhabov, N.P. Mankad, Org. Lett. 23 (2021) 3221–3226. doi: 10.1021/acs.orglett.1c00928
20. [20]
  A. Louka, M. Stratakis, Org. Lett. 23 (2021) 3599–3603. doi: 10.1021/acs.orglett.1c00997
21. [21]
  V. Debrauwer, A. Turlik, L. Rummler, et al., J. Am. Chem. Soc. 142 (2020) 11153–11164. doi: 10.1021/jacs.0c03556
22. [22]
  W. Lin, L. You, W. Yuan, C. He, ACS Catal. 12 (2022) 14592–14600. doi: 10.1021/acscatal.2c04571
23. [23]
  M. Itazaki, M. Kamitani, H. Nakazawa, Chem. Commun. 47 (2011) 7854. doi: 10.1039/c1cc12530c
24. [24]
  K. de la Vega-Hernández, E. Romain, A. Coffinet, et al., J. Am. Chem. Soc. 140 (2018) 17632–17642. doi: 10.1021/jacs.8b09851
25. [25]
  H. Liang, Y.X. Ji, R.H. Wang, Z.H. Zhang, B. Zhang, Org. Lett. 21 (2019) 2750–2754. doi: 10.1021/acs.orglett.9b00701
26. [26]
  Z. Li, Q. Sun, P. Qian, et al., Chin. Chem. Lett. 31 (2020) 1855–1858. doi: 10.1016/j.cclet.2020.02.030
27. [27]
  R. Lang, X. Du, Y. Huang, et al., Chem. Rev. 120 (2020) 11986–12043. doi: 10.1021/acs.chemrev.0c00797
28. [28]
  B. Geng, X. Chu, L. Liu, et al., Chin. Chem. Lett. 35 (2024) 108924. doi: 10.1016/j.cclet.2023.108924
29. [29]
  H. Hu, J. Xi, Chin. Chem. Lett. 34 (2023) 107959. doi: 10.1016/j.cclet.2022.107959
30. [30]
  V.B. Saptal, V. Ruta, M.A. Bajada, G. Vilé, Angew. Chem. Int. Ed. 62 (2023) e202219306. doi: 10.1002/anie.202219306
31. [31]
  H.T. Ji, Y.H. Lu, Y.T. Liu, et al., Chin. Chem. Lett. 36 (2025) 110568. doi: 10.1016/j.cclet.2024.110568
32. [32]
  H. Tang, H. Zhou, Y. Pan, J. et al., Angew. Chem. Int. Ed. 63 (2023) 202315032.
33. [33]
  W.Y. Huang, G.Q. Wang, W.H. Li, et al., Chem 6 (2020) 2300–2313. doi: 10.1016/j.chempr.2020.06.020
34. [34]
  B. Ye, W. Li, X. Zhang, et al., Adv. Mater. 36(2024), 2402747. doi: 10.1002/adma.202402747
35. [35]
  Z. Liu, F. Huang, M. Peng, et al., Nat. Commun. 12 (2021) 6194. doi: 10.1038/s41467-021-26542-y
36. [36]
  P. Gao, G. Liang, T. Ru, et al., Nat. Commun. 12 (2021) 4698. doi: 10.1038/s41467-021-25061-0
37. [37]
  W. Li, C. Li, H. Xiong, et al., Angew. Chem. Int. Ed. 58 (2019) 2448–2453. doi: 10.1002/anie.201814493
38. [38]
  X. He, Q. He, Y. Deng, et al., Nat. Commun. 10 (2019) 3663. doi: 10.1038/s41467-019-11619-6
39. [39]
  X. Liu, C. Wang, J. Meng, et al., Chin. Chem. Lett. 34 (2023) 108745. doi: 10.1016/j.cclet.2023.108745
40. [40]
  X. Li, J. Wang, Q. Yuan, et al., Angew. Chem. Int. Ed. 62 (2023) e202307570. doi: 10.1002/anie.202307570
41. [41]
  Q. Xu, C. Guo, B. Li, et al., J. Am. Chem. Soc. 144 (2022) 4321–4326. doi: 10.1021/jacs.2c01456
42. [42]
  W. Xue, Z. Zhu, S. Chen, B. You, C. Tang, J. Am. Chem. Soc. 145 (2023) 4142–4149. doi: 10.1021/jacs.2c12344
43. [43]
  K. Liu, B. Badamdorj, F. Yang, M.J. Janik, M. Antonietti, Angew. Chem. Int. Ed. 60 (2021) 24220–24226. doi: 10.1002/anie.202109689
44. [44]
  W. Li, B. Ye, J. Yang, et al., Angew. Chem. Int. Ed. 134 (2022) e202209749. doi: 10.1002/ange.202209749
45. [45]
  J.L. Sun, H. Jiang, P.H. Dixneuf, M. Zhang, J. Am. Chem. Soc. 145 (2023) 17329–17336. doi: 10.1021/jacs.3c04857
46. [46]
  X. Wang, Y. Wang, L. Cui, et al., Chin. Chem. Lett. 35 (2024) 110031. doi: 10.1016/j.cclet.2024.110031
47. [47]
  D. Wen, J. Chen, Q. Zheng, S. Yang, T. Tu, CCS Chem. 5 (2023) 1602–1611. doi: 10.31635/ccschem.022.202202233
48. [48]
  H. Wang, D. Xu, E. Guan, et al., ACS Catal. 10 (2020) 6299–6308. doi: 10.1021/acscatal.0c00485
49. [49]
  W.H. Li, J. Yang, H. Jing, et al., J. Am. Chem. Soc. 143 (2021) 15453–15461. doi: 10.1021/jacs.1c08088
50. [50]
  D.J. Durand, N. Fey, Chem. Rev. 119 (2019) 6561–6594. doi: 10.1021/acs.chemrev.8b00588
51. [51]
  R. Wei, S. Ju, L.L. Liu, Angew. Chem. Int. Ed. 61 (2022) e202205618. doi: 10.1002/anie.202205618
52. [52]
  L. Cheng, M.M. Li, M.L. Li, et al., CCS Chem. 4 (2022) 2612–2619. doi: 10.31635/ccschem.021.202101472
53. [53]
  P. Wang, P. Verma, G. Xia, et al., Nature 551 (2017) 489–493. doi: 10.1038/nature24632
54. [54]
  X. Wang, S. Wu, Y. Zhong, et al., Chin. Chem. Lett. 34 (2023) 107537. doi: 10.1016/j.cclet.2022.05.051
55. [55]
  G. Wang, Z. Ge, K. Ding, X. Wang, Angew. Chem. Int. Ed. 62 (2023) e202307973. doi: 10.1002/anie.202307973
56. [56]
  Q. Li, K. Yan, Y. Zhu, et al., Chin. Chem. Lett. 34 (2023) 108014. doi: 10.1016/j.cclet.2022.108014
57. [57]
  Y.N. Ma, S.X. Li, S.D. Yang, Acc. Chem. Res. 50 (2017) 1480–1492. doi: 10.1021/acs.accounts.7b00167
58. [58]
  S. Zhao, T. Gensch, B. Murray, et al., Science 362 (2018) 670–674. doi: 10.1126/science.aat2299
59. [59]
  S. Seo, J. Jung, H. Kim, Angew. Chem. Int. Ed. 62 (2023) e202303853. doi: 10.1002/anie.202303853
60. [60]
  P. Hu, L. Kong, F. Wang, X. Zhu, X. Li, Angew. Chem. Int. Ed. 60 (2021) 20424–20429. doi: 10.1002/anie.202106871
61. [61]
  B. Zhan, L. Wang, J. Luo, X. Lin, B. Shi, Angew. Chem. Int. Ed. 59 (2020) 3568–3572. doi: 10.1002/anie.201915674
62. [62]
  D. Wang, B. Dong, Y. Wang, et al., Nat. Commun. 10 (2019) 3539. doi: 10.1038/s41467-019-11420-5
63. [63]
  L.Q. Chen, C.F. Zhu, S. Zhang, et al., Chin. Chem. Lett. 34 (2023) 108398. doi: 10.1016/j.cclet.2023.108398
1. [1]
  Xinyuan Li , Zhuozhu Li , Wenzhong Huang , Jiantao Li , Wei Zhang , Shihao Feng , Hao Fan , Zhuo Chen , Sungsik Lee , Congcong Cai , Liang Zhou . Solvent-free synthesis of Co single atom and nanocluster decorated N-doped carbon for efficient oxygen reduction. Chinese Chemical Letters, 2025, 36(9): 110716-. doi: 10.1016/j.cclet.2024.110716
2. [2]
  Yuehai Zhi , Chen Gu , Huachao Ji , Kang Chen , Wenqi Gao , Jianmei Chen , Dafeng Yan . The advanced development of innovative photocatalytic coupling strategies for hydrogen production. Chinese Chemical Letters, 2025, 36(1): 110234-. doi: 10.1016/j.cclet.2024.110234
3. [3]
  Xue Zhao , Rui Zhao , Qian Liu , Henghui Chen , Jing Wang , Yongfeng Hu , Yan Li , Qiuming Peng , John S Tse . A p-d block synergistic effect enables robust electrocatalytic oxygen evolution. Chinese Chemical Letters, 2024, 35(11): 109496-. doi: 10.1016/j.cclet.2024.109496
4. [4]
  Baokang Geng , Xiang Chu , Li Liu , Lingling Zhang , Shuaishuai Zhang , Xiao Wang , Shuyan Song , Hongjie Zhang . High-efficiency PdNi single-atom alloy catalyst toward cross-coupling reaction. Chinese Chemical Letters, 2024, 35(7): 108924-. doi: 10.1016/j.cclet.2023.108924
5. [5]
  Yiwen Xu , Chaozheng He , Chenxu Zhao , Ling Fu . Single-atom Ti doping on S-vacancy two-dimensional CrS₂ as a catalyst for ammonia synthesis: A DFT study. Chinese Chemical Letters, 2025, 36(4): 109797-. doi: 10.1016/j.cclet.2024.109797
6. [6]
  Fan Chen , Xiaoyu Zhao , Weihang Miao , Yingying Li , Ye Yuan , Lingling Chu . Regio- and enantioselective hydrofluorination of internal alkenes via nickel-catalyzed hydrogen atom transfer. Chinese Chemical Letters, 2025, 36(5): 110239-. doi: 10.1016/j.cclet.2024.110239
7. [7]
  Qijun Tang , Wenguang Tu , Yong Zhou , Zhigang Zou . High efficiency and selectivity catalyst for photocatalytic oxidative coupling of methane. Chinese Journal of Structural Chemistry, 2023, 42(12): 100170-100170. doi: 10.1016/j.cjsc.2023.100170
8. [8]
  Liu Lin , Zemin Sun , Huatian Chen , Lian Zhao , Mingyue Sun , Yitao Yang , Zhensheng Liao , Xinyu Wu , Xinxin Li , Cheng Tang . Recent Advances in Electrocatalytic Two-Electron Water Oxidation for Green H₂O₂ Production. Acta Physico-Chimica Sinica, 2024, 40(4): 2305019-0. doi: 10.3866/PKU.WHXB202305019
9. [9]
  Min Liu , Di Wang , Zenghui Ye , Donghao Jiang , Bencan Tang , Yanqi Wu , Fengzhi Zhang . Highly stereo- and enantio-selective synthesis of spiro cyclopropyl oxindoles via organic catalyst-mediated cyclopropanation. Chinese Chemical Letters, 2025, 36(10): 110923-. doi: 10.1016/j.cclet.2025.110923
10. [10]
  Jinzhou Zheng , Chaozheng He , Chenxu Zhao . Rational catalyst design for N₂ electro-reduction: Regulation strategies and quick screen towards enhanced conversion efficiency. Chinese Chemical Letters, 2025, 36(7): 111056-. doi: 10.1016/j.cclet.2025.111056
11. [11]
  Zhili Yang , Liqun Liu , Xuebi Rao , Zeyu Jin , Jialin Sun , Yongkang Zhu , Shiming Zhang . Deprotonation effect doubles active site density in Fe-N₄-C catalyst for oxygen reduction electrocatalysis. Chinese Chemical Letters, 2025, 36(11): 111440-. doi: 10.1016/j.cclet.2025.111440
12. [12]
  Weichen Zhu , Wei Zuo , Pu Wang , Wei Zhan , Jun Zhang , Lipin Li , Yu Tian , Hong Qi , Rui Huang . Fe-N-C heterogeneous Fenton-like catalyst for the degradation of tetracycline: Fe-N coordination and mechanism studies. Chinese Chemical Letters, 2024, 35(9): 109341-. doi: 10.1016/j.cclet.2023.109341
13. [13]
  Xiangyang Ji , Yishuang Chen , Peng Zhang , Shaojia Song , Jian Liu , Weiyu Song . Boosting the first C–H bond activation of propane on rod-like V/CeO₂ catalyst by photo-assisted thermal catalysis. Chinese Chemical Letters, 2025, 36(5): 110719-. doi: 10.1016/j.cclet.2024.110719
14. [14]
  Xiujuan Wang , Yijie Wang , Luyun Cui , Wenqiang Gao , Xiao Li , Hong Liu , Weijia Zhou , Jingang Wang . Coordination-based synthesis of Fe single-atom anchored nitrogen-doped carbon nanofibrous membrane for CO₂ electroreduction with nearly 100% CO selectivity. Chinese Chemical Letters, 2024, 35(12): 110031-. doi: 10.1016/j.cclet.2024.110031
15. [15]
  Hong Yin , Zhipeng Yu . Hexavalent iridium catalyst enhances efficiency of hydrogen production. Chinese Journal of Structural Chemistry, 2025, 44(1): 100382-100382. doi: 10.1016/j.cjsc.2024.100382
16. [16]
  Zimo Peng , Quan Zhang , Gaocan Qi , Hao Zhang , Qian Liu , Guangzhi Hu , Jun Luo , Xijun Liu . Nanostructured Pt@RuOx catalyst for boosting overall acidic seawater splitting. Chinese Journal of Structural Chemistry, 2024, 43(1): 100191-100191. doi: 10.1016/j.cjsc.2023.100191
17. [17]
  Yizhe Chen , Yuzhou Jiao , Liangyu Sun , Cheng Yuan , Qian Shen , Peng Li , Shiming Zhang , Jiujun Zhang . Nonmetallic phosphorus alloying to regulate the oxygen reduction mechanisms of platinum catalyst. Chinese Chemical Letters, 2025, 36(4): 110789-. doi: 10.1016/j.cclet.2024.110789
18. [18]
  Lei Wan , Yizhou Tong , Xi Lu , Yao Fu . Cobalt-catalyzed reductive alkynylation to construct C(sp)-C(sp³) and C(sp)-C(sp²) bonds. Chinese Chemical Letters, 2024, 35(7): 109283-. doi: 10.1016/j.cclet.2023.109283
19. [19]
  Jiajun Wang , Guolin Yi , Shengling Guo , Jianing Wang , Shujuan Li , Ke Xu , Weiyi Wang , Shulai Lei . Computational design of bimetallic TM₂@g-C₉N₄ electrocatalysts for enhanced CO reduction toward C₂ products. Chinese Chemical Letters, 2024, 35(7): 109050-. doi: 10.1016/j.cclet.2023.109050
20. [20]
  Fengqing Wang , Changxing Qi , Chunmei Chen , Qin Li , Qingyi Tong , Weiguang Sun , Zhengxi Hu , Minyan Wang , Hucheng Zhu , Lianghu Gu , Yonghui Zhang . Discovery and enantioselective total synthesis of antitumor agent asperfilasin A via a regio- and diastereoselective Nazarov cyclization. Chinese Chemical Letters, 2025, 36(6): 110252-. doi: 10.1016/j.cclet.2024.110252

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(22)
HTML views(4)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142