Citation: Fuyang Yue, Mingxing Li, Fei Yuan, Hongjian Song, Yuxiu Liu, Qingmin Wang. Deboronative cross-coupling enabled by nickel metallaphotoredox catalysis[J]. Chinese Chemical Letters, ;2025, 36(12): 111053. doi: 10.1016/j.cclet.2025.111053 shu

Deboronative cross-coupling enabled by nickel metallaphotoredox catalysis

State Key Laboratory of Elemento-Organic Chemistry, Research Institute of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin 300071, China

wangqm@nankai.edu.cn

Received Date: 8 January 2025
Revised Date: 26 February 2025
Accepted Date: 6 March 2025
Available Online: 7 March 2025

Figures(5)

With advances in organoboron chemistry, boron-centered functional groups, especially alkyl boronic acids, which are widely available, bench stable, easy to prepare, minimally toxic, and structurally diverse, have become increasingly attractive. However, their utility is limited by their high oxidation potentials. In this study, we overcame this limitation by complexing an inorganic base (K₃PO₄) with alkyl boronic acids to decrease their oxidation potentials. Specifically, we present a powerful method for light-mediated deboronative cross-coupling reactions between alkyl boronic acids and aryl halides to afford products. This method demonstrated good functional group tolerance, and the mild conditions enabled the functionalization of drug molecules. In addition, the method could be extended to three-component carboacylation/carboarylation reactions of olefins to give products with high enantiomeric excess. Moreover, the reactions could be carried out under continuous-flow conditions, which enhanced the scalability, safety, and overall efficiency of the method.
- Deboronative,
- Metallaphotoredox,
- Enantioselective,
- Radicals,
- Nickel
1. [1]
  Z. Zhang, V. Gevorgyan, Chem. Rev. 124 (2024) 7214–7261. doi: 10.1021/acs.chemrev.3c00869
2. [2]
  S. Ni, R. Halder, D. Ahmadli, et al., Nat. Catal. 7 (2024) 733–741. doi: 10.1038/s41929-024-01160-1
3. [3]
  F. Yue, H. Ma, P. Ding, et al., ACS Cent. Sci. 9 (2023) 2268–2276. doi: 10.1021/acscentsci.3c00993
4. [4]
  F. Yue, M. Li, K. Yang, et al., Chem. Sci. 15 (2024) 14241–14247. doi: 10.1039/d4sc02889a
5. [5]
  D. Rana, P.M. Pflüger, N.P. Hölter, G. Tan, F. Glorius, ACS Cent. Sci. 10 (2024) 899–906.
6. [6]
  Y. Liang, T. Bian, K. Yadav, et al., ACS Cent. Sci. 10 (2024) 1191–1200. doi: 10.1021/acscentsci.4c00094
7. [7]
  M. Lu, J. Goh, M. Maraswami, et al., Chem. Rev. 122 (2022) 17479–17646. doi: 10.1021/acs.chemrev.2c00032
8. [8]
  W. Liu, P. Liu, L. Lv, C.J. Li, Angew. Chem. Int. Ed. 57 (2018) 13499–13503. doi: 10.1002/anie.201807181
9. [9]
  D. Zheng, A. Studer, Angew. Chem. Int. Ed. 131 (2019) 15950–15954. doi: 10.1002/ange.201908987
10. [10]
  Y. Chen, X. Wang, X. He, Q. An, Z. Zuo, J. Am. Chem. Soc. 143 (2021) 4896–4902. doi: 10.1021/jacs.1c00618
11. [11]
  C. Zhu, H. Yue, L. Chu, M. Rueping, Chem. Sci. 11 (2020) 4051–4064. doi: 10.1039/d0sc00712a
12. [12]
  F. Song, F. Wang, L. Guo, et al., Angew. Chem. Int. Ed. 59 (2020) 177–181. doi: 10.1002/anie.201909543
13. [13]
  J. Khamrai, I. Ghosh, A. Savateev, M. Antonietti, B. König, ACS Catal. 10 (2020) 3526–3532. doi: 10.1021/acscatal.9b05598
14. [14]
  L. Huang, T. Ji, M. Rueping, J. Am. Chem. Soc. 142 (2020) 3532–3539. doi: 10.1021/jacs.9b12490
15. [15]
  M.S. Oderinde, M. Frenette, D.W. Robbins, B. Aquila, J.W. Johannes, J. Am. Chem. Soc. 138 (2016) 1760–1763. doi: 10.1021/jacs.5b11244
16. [16]
  X. Lang, J. Zhao, X. Chen, Chem. Soc. Rev. 45 (2016) 3026–3038. doi: 10.1039/C5CS00659G
17. [17]
  K.L. Skubi, T.R. Blum, T.P. Yoon, Chem. Rev. 116 (2016) 10035–10074. doi: 10.1021/acs.chemrev.6b00018
18. [18]
  C.K. Prier, D.A. Rankic, D.W.C. MacMillan, Chem. Rev. 113 (2013) 5322–5363. doi: 10.1021/cr300503r
19. [19]
  J.K. Matsui, S.B. Lang, D.R. Heitz, G.A. Molander, ACS Catal. 7 (2017) 2563–2575. doi: 10.1021/acscatal.7b00094
20. [20]
  K.J. Romero, M.S. Galliher, D.A. Pratt, C.R.J. Stephenson, Chem. Soc. Rev. 47 (2018) 7851–7866. doi: 10.1039/c8cs00379c
21. [21]
  L. Buzzetti, A. Prieto, S.R. Roy, P. Melchiorre, Angew. Chem. Int. Ed. 56 (2017) 15039–15043. doi: 10.1002/anie.201709571
22. [22]
  R.A. Garza-Sanchez, A. Tlahuext-Aca, G. Tavakoli, F. Glorius, ACS Catal. 7 (2017) 4057–4061. doi: 10.1021/acscatal.7b01133
23. [23]
  I.B. Perry, T.F. Brewer, P.J. Sarver, et al., Nature 560 (2018) 70–75. doi: 10.1038/s41586-018-0366-x
24. [24]
  D. Ravelli, S. Protti, M. Fagnoni, Acc. Chem. Res. 49 (2016) 2232–2242. doi: 10.1021/acs.accounts.6b00339
25. [25]
  A. Luridiana, D. Mazzarella, L. Capaldo, et al., ACS Catal. 12 (2022) 11216–11225. doi: 10.1021/acscatal.2c03805
26. [26]
  F. Juliá, T. Constantin, D. Leonori, Chem. Rev. 122 (2022) 2292–2352. doi: 10.1021/acs.chemrev.1c00558
27. [27]
  V. Bacauanu, S. Cardinal, M. Yamauchi, et al., Angew. Chem. Int. Ed. 57 (2018) 12543–12548. doi: 10.1002/anie.201807629
28. [28]
  Q.Q. Zhou, S.J.S. Dü sel, L.Q. Lu, B. König, W.J. Xiao, Chem. Commun. 55 (2019) 107–110. doi: 10.1039/c8cc08362b
29. [29]
  M.W. Campbell, J.S. Compton, C.B. Kelly, G.A. Molander, J. Am. Chem. Soc. 141 (2019) 20069–20078. doi: 10.1021/jacs.9b08282
30. [30]
  A. García-Domínguez, R. Mondal, C. Nevado, Angew. Chem. Int. Ed. 58 (2019) 12286–12290. doi: 10.1002/anie.201906692
31. [31]
  S. Xu, H. Chen, Z. Zhou, W. Kong, Angew. Chem. Int. Ed. 60 (2021) 7405–7411. doi: 10.1002/anie.202014632
32. [32]
  M.W. Campbell, M. Yuan, V.C. Polites, O. Gutierrez, G.A. Molander, J. Am. Chem. Soc. 143 (2021) 3901–3910. doi: 10.1021/jacs.0c13077
33. [33]
  R. Zhang, G. Li, M. Wismer, et al., ACS Med. Chem. Lett. 9 (2018) 773–777. doi: 10.1021/acsmedchemlett.8b00183
34. [34]
  P. Li, J.A. Terrett, J.R. Zbieg, ACS Med. Chem. Lett. 11 (2020) 2120–2130. doi: 10.1021/acsmedchemlett.0c00436
35. [35]
  S.R. Chemler, D. Trauner, S.J. Danishefsky, Angew. Chem. Int. Ed. 40 (2001) 4544–4568. doi: 10.1002/1521-3773(20011217)40:24<4544::AID-ANIE4544>3.0.CO;2-N
36. [36]
  R. Jana, T.P. Pathak, M.S. Sigman, Chem. Rev. 111 (2011) 1417–1492. doi: 10.1021/cr100327p
37. [37]
  G.A. Molander, T. Ito, Org. Lett. 3 (2001) 393–396. doi: 10.1021/ol006896u
38. [38]
  B. Wang, H.X. Sun, Z.H. Sun, G.Q. Lin, Adv. Synth. Catal. 351 (2009) 415–422. doi: 10.1002/adsc.200800630
39. [39]
  J.C. Tellis, D.N. Primer, G.A. Molander, Science 345 (2014) 433–436. doi: 10.1126/science.1253647
40. [40]
  Y. Yasu, T. Koike, M. Akita, Adv. Synth. Catal. 354 (2012) 3414–3420. doi: 10.1002/adsc.201200588
41. [41]
  F. Lima, M.A. Kabeshov, D.N. Tran, et al., Angew. Chem. Int. Ed. 55 (2016) 14085–14089. doi: 10.1002/anie.201605548
42. [42]
  C. Shu, A. Noble, V.K. Aggarwal, Angew. Chem. Int. Ed. 58 (2019) 3870–3874. doi: 10.1002/anie.201813917
43. [43]
  D. Kaiser, A. Noble, V. Fasano, V.K. Aggarwal, J. Am. Chem. Soc. 141 (2019) 14104–14109. doi: 10.1021/jacs.9b07564
44. [44]
  Y. Sato, K. Nakamura, Y. Sumida, et al., J. Am. Chem. Soc. 142 (2020) 9938–9943. doi: 10.1021/jacs.0c04456
45. [45]
  E. Speckmeier, T.C. Maier, J. Am. Chem. Soc. 144 (2022) 9997–10005. doi: 10.1021/jacs.2c03220
46. [46]
  T. Wan, L. Capaldo, J. Djossou, et al., Nat Commun. 15 (2024) 4028. doi: 10.1038/s41467-024-48212-5
47. [47]
  S. Pillitteri, P. Ranjan, E.V. Van der Eycken, U.K. Sharma, Adv. Synth. Catal. 364 (2022) 1643–1665. doi: 10.1002/adsc.202200204
48. [48]
  F. Yue, H. Ma, H. Song, et al., Chem. Sci. 13 (2022) 13466–13474. doi: 10.1039/d2sc05521j
49. [49]
  Z. Dong, D.W.C. MacMillan, Nature 598 (2021) 451–456. doi: 10.1038/s41586-021-03920-6
50. [50]
  P.J. Harrington, E. Lodewijk, Org. Process Res. Dev. 1 (1997) 72–76. doi: 10.1021/op960009e
51. [51]
  L. Guo, M. Yuan, Y. Zhang, et al., J. Am. Chem. Soc. 142 (2020) 20390–20399. doi: 10.1021/jacs.0c08823
52. [52]
  P. Qian, H. Guan, Y.E. Wang, et al., Nat. Commun. 12 (2021) 6613–6621. doi: 10.1038/s41467-021-26794-8
53. [53]
  X. Du, I. Cheng-Sánchez, C. Nevado, J. Am. Chem. Soc. 145 (2023) 12532–12540. doi: 10.1021/jacs.3c00744
54. [54]
  M.S. Liu, W. Shu, JACS Au 3 (2023) 1321–1327. doi: 10.1021/jacsau.3c00069
55. [55]
  J.L. Jat, P. Kumar, S. Verma, et al., New J. Chem. 46 (2022) 14782–14785. doi: 10.1039/d2nj02755k
56. [56]
  S. Song, X. Li, X. Sun, Y. Yuan, N. Jiao, Green Chem. 17 (2015) 3285–3289. doi: 10.1039/C5GC00528K
57. [57]
  J. Kim, J. Kim, S. Chang, Chem. Eur. J. 19 (2013) 7328–7333. doi: 10.1002/chem.201301025
58. [58]
  Z. Shi, M. Boultadakis-Arapinis, F. Glorius, Chem. Commun. 49 (2013) 6489–6491. doi: 10.1039/c3cc43903h
59. [59]
  A.R. Schmitzer, S. Franceschi, E. Perez, et al., J. Am. Chem. Soc. 123 (2001) 5956–5961. doi: 10.1021/ja000378x
60. [60]
  Y.F. Liang, N. Jiao, Angew. Chem. Int. Ed. 53 (2014) 548–552. doi: 10.1002/anie.201308698
61. [61]
  Y.J. Mao, B.X. Wang, Q.Z. Wu, et al., Chem. Commun. 55 (2019) 2019–2022. doi: 10.1039/c8cc09129c
62. [62]
  H. Lee, Y.K. Sim, J.W. Park, C.H. Jun, Chem. Eur. J. 20 (2014) 323–333. doi: 10.1002/chem.201302699
63. [63]
  A. Long, C.J. Oswood, C.B. Kelly, M.C. Bryan, D.W.C. MacMillan, Nature 628 (2024) 326–332. doi: 10.1038/s41586-024-07181-x
64. [64]
  W. Li, Y. Wu, S. Li, et al., J. Am. Chem. Soc. 144 (2022) 8551–8559. doi: 10.1021/jacs.1c12463
1. [1]
  Jiangping Chen , Hongju Ren , Kai Wu , Huihuang Fang , Chongqi Chen , Li Lin , Yu Luo , Lilong Jiang . Boosting hydrogen production of ammonia decomposition via the construction of metal-oxide interfaces. Chinese Journal of Structural Chemistry, 2024, 43(2): 100236-100236. doi: 10.1016/j.cjsc.2024.100236
2. [2]
  Pengfei Li , Chulin Qu , Fan Wu , Hu Gao , Chengyan Zhao , Yue Zhao , Zhen Shen . Robust free-base and metalated corrole radicals with reduction-induced emission. Chinese Chemical Letters, 2025, 36(2): 110292-. doi: 10.1016/j.cclet.2024.110292
3. [3]
  Yujia Shi , Yan Qiao , Pengfei Xie , Miaomiao Tian , Xingwei Li , Junbiao Chang , Bingxian Liu . Rhodium-catalyzed enantioselective in situ C(sp³)−H heteroarylation by a desymmetrization approach. Chinese Chemical Letters, 2024, 35(10): 109544-. doi: 10.1016/j.cclet.2024.109544
4. [4]
  Shuai Zhu , Mingjie Chen , Haichao Shen , Hanming Ding , Wenbo Li , Junliang Zhang . Palladium/Xu-Phos-catalyzed enantioselective arylalkoxylation reaction of γ-hydroxyalkenes at room temperature. Chinese Chemical Letters, 2024, 35(11): 109879-. doi: 10.1016/j.cclet.2024.109879
5. [5]
  Zhenkang Ai , Hui Chen , Xuebin Liao . Nickel-catalyzed decarboxylative difluoromethylation and alkylation of alkenes. Chinese Chemical Letters, 2025, 36(3): 109954-. doi: 10.1016/j.cclet.2024.109954
6. [6]
  Xiao-Bo Liu , Ren-Ming Liu , Xiao-Di Bao , Hua-Jian Xu , Qi Zhang , Yu-Feng Liang . Nickel-catalyzed reductive formylation of aryl halides via formyl radical. Chinese Chemical Letters, 2024, 35(12): 109783-. doi: 10.1016/j.cclet.2024.109783
7. [7]
  Shaobin He , Xiaoyun Guo , Qionghua Zheng , Huanran Shen , Yuan Xu , Fenglin Lin , Jincheng Chen , Haohua Deng , Yiming Zeng , Wei Chen . Engineering nickel-supported osmium bimetallic nanozymes with specifically improved peroxidase-like activity for immunoassay. Chinese Chemical Letters, 2025, 36(4): 110096-. doi: 10.1016/j.cclet.2024.110096
8. [8]
  Xinghao Cai , Chen Ma , Ying Kang , Yuqiang Ren , Xue Meng , Wei Lu , Shiming Fan , Shouxin Liu . Nickel-catalyzed C(sp²)–H alkynylation of free α-substituted benzylamines using a transient directing group. Chinese Chemical Letters, 2025, 36(10): 110901-. doi: 10.1016/j.cclet.2025.110901
9. [9]
  Zhirong Yang , Shan Wang , Ming Jiang , Gengchen Li , Long Li , Fangzhi Peng , Zhihui Shao . One stone three birds: Ni-catalyzed asymmetric allenylic substitution of allenic ethers, hydroalkylation of 1,3-enynes and double alkylation of enynyl ethers. Chinese Chemical Letters, 2024, 35(8): 109518-. doi: 10.1016/j.cclet.2024.109518
10. [10]
  Tengfei Xuan , Yuan Pan , Zhenyu Shi , Yang Wang . Organocatalytic asymmetric synthesis of oxazolines from N-acylimines. Chinese Chemical Letters, 2025, 36(6): 110352-. doi: 10.1016/j.cclet.2024.110352
11. [11]
  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
12. [12]
  Xingfen Huang , Jiefeng Zhu , Chuan He . Catalytic enantioselective N-silylation of sulfoximine. Chinese Chemical Letters, 2024, 35(4): 108783-. doi: 10.1016/j.cclet.2023.108783
13. [13]
  Chong Wang , Hao Xie , Rulan Xia , Xuewei Liao , Jin Wang , Huajun Yang , Chen Wang . Nanofluidic ion rectification sensor for enantioselective recognition and detection. Chinese Chemical Letters, 2025, 36(8): 110642-. doi: 10.1016/j.cclet.2024.110642
14. [14]
  Jindan Zhang , Zhenghong Li , Chi Li , Mengqi Zhu , Shicheng Tang , Kaicong Cai , Zhibin Cheng , Chulong Liu , Shengchang Xiang , Zhangjing Zhang . Revealing a new doping mechanism of spiro-OMeTAD with tBP participation through the introduction of radicals into HTM. Chinese Chemical Letters, 2025, 36(3): 110046-. doi: 10.1016/j.cclet.2024.110046
15. [15]
  Xuan Song , Teng Fu , Yajie Yang , Yahan Kuang , Xiuli Wang , Yu-Zhong Wang . Spatial-confinement combustion strategy enabling free radicals chemiluminescence direct-measurement in flame-retardant mechanism. Chinese Chemical Letters, 2025, 36(5): 110699-. doi: 10.1016/j.cclet.2024.110699
16. [16]
  Yusong Bi , Rongzhen Zhang , Kaikai Niu , Shengsheng Yu , Hui Liu , Lingbao Xing . Construction of a three-step sequential energy transfer system with selective enhancement of superoxide anion radicals for photocatalysis. Chinese Chemical Letters, 2025, 36(5): 110311-. doi: 10.1016/j.cclet.2024.110311
17. [17]
  Jingjing Zhang , Fei Yang , Liying Zhang , Ran Li , Guo Wang , Yanqing Xu , Wei Wei . Stable radicals in bacteria composites hybridized by a doubly-strapped perylene diimide for near-infrared photothermal conversion. Chinese Chemical Letters, 2025, 36(7): 110627-. doi: 10.1016/j.cclet.2024.110627
18. [18]
  Ying Zhao , Yao He , Jian-Xin Yang , Wen-Jie Liu , Dan Tian , Francisco Aznarez , Le-Le Gong , Li-Long Dang , Lu-Fang Ma . Controllable self-assembly and photothermal conversion of metalla[2]catenanes induced by synergistic effect of free radicals and stacking interactions. Chinese Chemical Letters, 2025, 36(12): 111460-. doi: 10.1016/j.cclet.2025.111460
19. [19]
  Minghui Zhang , Na Zhang , Qian Zhao , Chao Wang , Alexander Steiner , Jianliang Xiao , Weijun Tang . Cobalt pincer complex-catalyzed highly enantioselective hydrogenation of quinoxalines. Chinese Chemical Letters, 2025, 36(4): 110081-. doi: 10.1016/j.cclet.2024.110081
20. [20]
  Yanxin Jiang , Kwai Wun Cheng , Zhiping Yang , Jun (Joelle) Wang . Pd-catalyzed enantioselective and regioselective asymmetric hydrophosphorylation and hydrophosphinylation of enynes. Chinese Chemical Letters, 2025, 36(5): 110231-. doi: 10.1016/j.cclet.2024.110231

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(21)
HTML views(5)

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