Citation: Shan-Xiu Ni, Yan-Lin Li, Hui-Qi Ni, Yu-Xiang Bi, Jie Sheng, Xi-Sheng Wang. Nickel-catalyzed hydromonofluoromethylation of unactivated alkenes for expedient construction of primary alkyl fluorides[J]. Chinese Chemical Letters, ;2023, 34(3): 107614. doi: 10.1016/j.cclet.2022.06.037 shu

Nickel-catalyzed hydromonofluoromethylation of unactivated alkenes for expedient construction of primary alkyl fluorides

Department of Chemistry, University of Science and Technology of China, Hefei 230026, China

xswang77@ustc.edu.cn

Received Date: 24 April 2022
Revised Date: 13 June 2022
Accepted Date: 14 June 2022
Available Online: 18 June 2022

Figures(6)

A nickel-catalyzed direct hydromonofluoromethylation of unactivated olefins with industrial raw fluoroiodomethane is developed, furnishing various primary alkyl fluorides in a step-economic manner. The key factor to success is the use of pyridine-oxazoline as ligand and (MeO)₂MeSiH as the hydrogen source. This transformation demonstrates high efficiency, mild conditions, good functional-group compatibility and great potential in the drug discovery.
- Hydromonofluoromethylation,
- Unactivated alkenes,
- Nickel-catalysis,
- Primary fluorides,
- Ni-H species
1. [1]
  C. Ni, J. Hu, Chem. Soc. Rev. 45 (2016) 5441–5454. doi: 10.1039/C6CS00351F
2. [2]
  R. Berger, G. Resnati, P. Metrangolo, et al., Chem. Soc. Rev. 40 (2011) 3496–3508. doi: 10.1039/c0cs00221f
3. [3]
  M.C. Walker, M.C.Y. Chang, Chem. Soc. Rev. 43 (2014) 6527–6536. doi: 10.1039/C4CS00027G
4. [4]
  J. Wang, M. Sanchez-Rosello, J.L. Acena, et al., Chem. Rev. 114 (2014) 2432–2506. doi: 10.1021/cr4002879
5. [5]
  N.A.J. Meanwell, Med. Chem. 61 (2018) 5822–5880. doi: 10.1021/acs.jmedchem.7b01788
6. [6]
  T. Liang, C.N. Neumann, T. Ritter, Angew. Chem. Int. Ed. 52 (2013) 8214–8264. doi: 10.1002/anie.201206566
7. [7]
  M.G. Campbell, T. Ritter, Chem. Rev. 115 (2015) 612–633. doi: 10.1021/cr500366b
8. [8]
  D.A. Petrone, J. Ye, M. Lautens, Chem. Rev. 116 (2016) 8003–8104. doi: 10.1021/acs.chemrev.6b00089
9. [9]
  S. Barata-Vallejo, M.V. Cooke, A. Postigo, ACS Catal. 8 (2018) 7287–7307. doi: 10.1021/acscatal.8b02066
10. [10]
  R. Szpera, D.F.J. Moseley, L.B. Smith, et al., Angew. Chem. Int. Ed. 58 (2019) 14824–14848. doi: 10.1002/anie.201814457
11. [11]
  M. Reichel, K. Karaghiosoff, Angew. Chem. 132 (2020) 12364–12377. doi: 10.1002/ange.201913175
12. [12]
  G.S. Lal, G.P. Pez, R.J. Pesaresi, et al., J. Org. Chem. 64 (1999) 7048–7054. doi: 10.1021/jo990566+
13. [13]
  H. Dang, M. Mailig, G. Lalic, Angew. Chem. Int. Ed. 53 (2014) 6473–6476. doi: 10.1002/anie.201402238
14. [14]
  J. Guo, C. Kuang, J. Rong, et al., Chem. Eur. J. 25 (2019) 7259–7264. doi: 10.1002/chem.201901176
15. [15]
  V. Fasano, N. Winter, A. Noble, et al., Angew. Chem. Int. Ed. 59 (2020) 8502–8506. doi: 10.1002/anie.202002246
16. [16]
  Y. Li, C. Ni, J. Liu, et al., Org. Lett. 8 (2006) 1693–1696. doi: 10.1021/ol060322t
17. [17]
  J. Liu, L. Zhang, J. Hu, Org. Lett. 10 (2008) 5377–5380. doi: 10.1021/ol802226k
18. [18]
  K. Matsuzaki, T. Furukawa, E. Tokunaga, et al., Org. Lett. 15 (2013) 3282–3285. doi: 10.1021/ol4013102
19. [19]
  Y. Geng, A. Liang, X. Gao, et al., J. Org. Chem. 82 (2017) 8604–8610. doi: 10.1021/acs.joc.7b01438
20. [20]
  G. Parisi, M. Colella, S. Monticelli, et al., J. Am. Chem. Soc. 139 (2017) 13648–13651. doi: 10.1021/jacs.7b07891
21. [21]
  G.K.S. Prakash, I. Ledneczki, S. Chacko, et al., Org. Lett. 10 (2008) 557–560. doi: 10.1021/ol702500u
22. [22]
  Y. Zhao, B. Gao, C. Ni, et al., Org. Lett. 14 (2012) 6080–6083. doi: 10.1021/ol3029737
23. [23]
  H. Doi, I. Ban, A. Nonoyama, et al., Chem. Eur. J. 15 (2009) 4165–4171. doi: 10.1002/chem.200801974
24. [24]
  N.Y. Wu, X.H. Xu, F.L. Qing, ACS Catal. 9 (2019) 5726–5731. doi: 10.1021/acscatal.9b01530
25. [25]
  Y. Cao, L. Jiang, W. Yi, Adv. Synth. Catal. 361 (2019) 4360–4368. doi: 10.1002/adsc.201900480
26. [26]
  X. Shen, M. Zhou, C. Ni, et al., Chem. Sci. 5 (2014) 117–122. doi: 10.1039/C3SC51831K
27. [27]
  Z. He, P. Tan, C. Ni, et al., Org. Lett. 17 (2015) 1838–1841. doi: 10.1021/acs.orglett.5b00308
28. [28]
  N. Noto, T. Koike, M. Akita, ACS Catal. 9 (2019) 4382–4387. doi: 10.1021/acscatal.9b00473
29. [29]
  X. Jiang, S. Sakthivel, K. Kulbitski, et al., J. Am. Chem. Soc. 136 (2014) 9548–9551. doi: 10.1021/ja504089y
30. [30]
  X. Jiang, M. Gandelman, J. Am. Chem. Soc. 137 (2015) 2542–2547. doi: 10.1021/jacs.5b00473
31. [31]
  Y.M. Su, G.S. Feng, Z.Y. Wang, et al., Angew. Chem. Int. Ed. 54 (2015) 6003–6007. doi: 10.1002/anie.201412026
32. [32]
  J. Sheng, H.Q. Ni, H.R. Zhang, et al., Angew. Chem. Int. Ed. 57 (2018) 7634–7639. doi: 10.1002/anie.201803228
33. [33]
  J. Sheng, H.Q. Ni, S.X. Ni, et al., Angew. Chem. Int. Ed. 60 (2021) 15020–15027. doi: 10.1002/anie.202102481
34. [34]
  R. Cu, J. Sheng, B.B. Wu, et al., Chem. Commun. 57 (2021) 9084–9087. doi: 10.1039/D1CC02837E
35. [35]
  Y.L. Li, W. Liu, Z.Y. Liu, CCS Chem. 3 (2021) 3320–3328.
36. [36]
  C.J. DeSantis, S.E. Skrabalak, J. Am. Chem. Soc. 135 (2013) 3989–3996. doi: 10.1021/ja312271c
37. [37]
  X. Wu, F.A. Cruz, A. Lu, et al., J. Am. Chem. Soc. 140 (2018) 10126–10130. doi: 10.1021/jacs.8b06069
38. [38]
  X. Li, J. Jin, P. Chen, Nat. Chem. 14 (2022) 425–432. doi: 10.1038/s41557-021-00869-x
39. [39]
  M. Arlt, O. Hindsgaul, J. Org. Chem. 60 (1995) 4617–4628. doi: 10.1021/jo00119a045
40. [40]
  Q. Liu, Y. Lu, H. Sheng, et al., Angew. Chem. Int. Ed. 60 (2021) 25477–25484. doi: 10.1002/anie.202111006
41. [41]
  Y. Zhang, B. Han, S. Zhu, Angew. Chem. Int. Ed. 58 (2019) 13860–13864. doi: 10.1002/anie.201907185
42. [42]
  Y. He, C. Liu, L. Yu, et al., Angew. Chem. Int. Ed. 59 (2020) 9186–9191. doi: 10.1002/anie.202001742
43. [43]
  D. Qian, Sr. Bera, X. Hu, J. Am. Chem. Soc. 143 (2021) 1959–1967. doi: 10.1021/jacs.0c11630
44. [44]
  Y. Cheng, Z. Gui, R. Tao, et al., Green Synth. Catal. 3 (2022) 377–379. doi: 10.1016/j.gresc.2022.03.009
45. [45]
  Y. He, Y. Cai, S. Zhu, J. Am. Chem. Soc. 139 (2017) 1061–1064. doi: 10.1021/jacs.6b11962
46. [46]
  Z.Y. Wang, G.H. Wan, G.Y. Wang, et al., Tetrahedron Lett. 59 (2018) 2302–2305. doi: 10.1016/j.tetlet.2018.05.008
47. [47]
  Z. Wang, H. Yin, G.C. Fu, Nature 563 (2018) 379–383. doi: 10.1038/s41586-018-0669-y
48. [48]
  S. Wang, J.X. Zhang, T.Y. Zhang, et al., Nat. Commun. 12 (2021) 2771–2780. doi: 10.1038/s41467-021-22983-7
49. [49]
  W. Guo, L. Cheng, G. Ma, et al., Org. Lett. 24 (2022) 1796–1801. doi: 10.1021/acs.orglett.2c00148
1. [1]
  Jian Han , Li-Li Zeng , Qin-Yu Fei , Yan-Xiang Ge , Rong-Hui Huang , Fen-Er Chen . Recent advances in remote C(sp³)–H functionalization via chelating group-assisted metal-catalyzed chain-walking reaction. Chinese Chemical Letters, 2024, 35(11): 109647-. doi: 10.1016/j.cclet.2024.109647
2. [2]
  Haoran Shi , Jiaxin Wang , Yuqin Zhu , Hongyang Li , Guodong Ju , Lanlan Zhang , Chao Wang . Highly selective α-C(sp³)-H arylation of alkenyl amides via nickel chain-walking catalysis. Chinese Chemical Letters, 2024, 35(7): 109333-. doi: 10.1016/j.cclet.2023.109333
3. [3]
  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
4. [4]
  Xiao-Ming Chen , Lianhui Song , Jun Pan , Fei Zeng , Yi Xie , Wei Wei , Dong Yi . Visible-light-induced four-component difunctionalization of alkenes to construct phosphorodithioate-containing quinoxalin-2(1H)-ones. Chinese Chemical Letters, 2024, 35(11): 110112-. doi: 10.1016/j.cclet.2024.110112
5. [5]
  Ruilong Geng , Lingzi Peng , Chang Guo . Dynamic kinetic stereodivergent transformations of propargylic ammonium salts via dual nickel and copper catalysis. Chinese Chemical Letters, 2024, 35(8): 109433-. doi: 10.1016/j.cclet.2023.109433
6. [6]
  Junxin Li , Chao Chen , Yuzhen Dong , Jian Lv , Jun-Mei Peng , Yuan-Ye Jiang , Daoshan Yang . Ligand-promoted reductive coupling between aryl iodides and cyclic sulfonium salts by nickel catalysis. Chinese Chemical Letters, 2024, 35(11): 109732-. doi: 10.1016/j.cclet.2024.109732
7. [7]
  Yi Luo , Lin Dong . Multicomponent remote C(sp²)-H bond addition by Ru catalysis: An efficient access to the alkylarylation of 2H-imidazoles. Chinese Chemical Letters, 2024, 35(10): 109648-. doi: 10.1016/j.cclet.2024.109648
8. [8]
  Li Li , Zhi-Xin Yan , Chuan-Kun Ran , Yi Liu , Shuo Zhang , Tian-Yu Gao , Long-Fei Dai , Li-Li Liao , Jian-Heng Ye , Da-Gang Yu . Electro-reductive carboxylation of CCl bonds in unactivated alkyl chlorides and polyvinyl chloride with CO₂. Chinese Chemical Letters, 2024, 35(12): 110104-. doi: 10.1016/j.cclet.2024.110104
9. [9]
  Kun Tang , Fen Su , Shijie Pan , Fengfei Lu , Zhongfu Luo , Fengrui Che , Xingxing Wu , Yonggui Robin Chi . Enones from aldehydes and alkenes by carbene-catalyzed dehydrogenative couplings. Chinese Chemical Letters, 2024, 35(9): 109495-. doi: 10.1016/j.cclet.2024.109495
10. [10]
  Er-Meng Wang , Ziyi Wang , Xu Ban , Xiaowei Zhao , Yanli Yin , Zhiyong Jiang . Chemoselective photocatalytic sulfenylamination of alkenes with sulfenamides via energy transfer. Chinese Chemical Letters, 2024, 35(12): 109843-. doi: 10.1016/j.cclet.2024.109843
11. [11]
  Peng Wang , Jianjun Wang , Ni Song , Xin Zhou , Ming Li . Radical dehydroxymethylative fluorination of aliphatic primary alcohols and diverse functionalization of α-fluoroimides via BF₃·OEt₂-catalyzed C‒F bond activation. Chinese Chemical Letters, 2025, 36(1): 109748-. doi: 10.1016/j.cclet.2024.109748
12. [12]
  Boqiang Wang , Yongzhuo Xu , Jiajia Wang , Muyang Yang , Guo-Jun Deng , Wen Shao . Transition-metal free trifluoromethylimination of alkenes enabled by direct activation of N-unprotected ketimines. Chinese Chemical Letters, 2024, 35(9): 109502-. doi: 10.1016/j.cclet.2024.109502
13. [13]
  Yunqiang Li , Yongxian Huang , Sinuo Li , He Huang , Zhiwei Jiao . Elaborating azaaryl alkanes enabled by photoredox/palladium dual catalyzed dialkylation of azaaryl alkenes. Chinese Chemical Letters, 2025, 36(4): 110051-. doi: 10.1016/j.cclet.2024.110051
14. [14]
  Conghui Wang , Lei Xu , Zhenhua Jia , Teck-Peng Loh . Recent applications of macrocycles in supramolecular catalysis. Chinese Chemical Letters, 2024, 35(4): 109075-. doi: 10.1016/j.cclet.2023.109075
15. [15]
  Wei Chen , Pieter Cnudde . A minireview to ketene chemistry in zeolite catalysis. Chinese Journal of Structural Chemistry, 2024, 43(11): 100412-100412. doi: 10.1016/j.cjsc.2024.100412
16. [16]
  Lin Zhang , Chaoran Li , Thongthai Witoon , Xingda An , Le He . Nano-thermometry in photothermal catalysis. Chinese Journal of Structural Chemistry, 2025, 44(4): 100456-100456. doi: 10.1016/j.cjsc.2024.100456
17. [17]
  Huaixiang Yang , Miao-Miao Li , Aijun Zhang , Jiefei Guo , Yongqi Yu , Wei Ding . Visible-light-induced photocatalyst- and metal-free radical phosphinoyloximation of alkenes with tert-butyl nitrite as bifunctional reagent. Chinese Chemical Letters, 2025, 36(3): 110425-. doi: 10.1016/j.cclet.2024.110425
18. [18]
  Yu Mao , Yilin Liu , Xiaochen Wang , Shengyang Ni , Yi Pan , Yi Wang . Acylfluorination of enynes via phosphine and silver catalysis. Chinese Chemical Letters, 2024, 35(8): 109443-. doi: 10.1016/j.cclet.2023.109443
19. [19]
  Jiaqi Jia , Kathiravan Murugesan , Chen Zhu , Huifeng Yue , Shao-Chi Lee , Magnus Rueping . Multiphoton photoredox catalysis enables selective hydrodefluorinations. Chinese Chemical Letters, 2025, 36(2): 109866-. doi: 10.1016/j.cclet.2024.109866
20. [20]
  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

Get Citation

PDF

XML

Metrics

PDF Downloads(5)
Abstract views(427)
HTML views(43)

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