Citation: Huai-Gui Li, Can-Ming Zhu, Weidong Yuan, Hongyi Chen, Zhengyuan Bo, Chao Deng, Yingguang Zhu, Kang Chen, Qing-Yuan Meng. Stereodivergent reductive C(sp²)-C(sp³) coupling between cycloketone oximes and vinyl halides enabled by tunable photoredox/Ti dual catalysis[J]. Chinese Chemical Letters, ;2026, 37(7): 111941. doi: 10.1016/j.cclet.2025.111941 shu

Stereodivergent reductive C(sp²)-C(sp³) coupling between cycloketone oximes and vinyl halides enabled by tunable photoredox/Ti dual catalysis

Huai-Gui Li ^{a, b, c, 1} ,
Can-Ming Zhu ^{b, c, 1} ,
Weidong Yuan ^a ,
Hongyi Chen ^a ,
Zhengyuan Bo ^a ,
Chao Deng ^{a, *,} ,
Yingguang Zhu ^{a, *,} ,
Kang Chen ^{a, *,} ,
Qing-Yuan Meng ^{b, c, *,}

a.
Jiangsu Key Laboratory of Pesticide Science and Department of Chemistry, College of Sciences, Nanjing Agricultural University, Nanjing 210095, China
b.
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
c.
University of Chinese Academy of Sciences, Beijing 100049, China

chaodeng@njau.edu.cn

ygzhu@njau.edu.cn

kchen@njau.edu.cn

mengqingyuan@iccas.ac.cn

Received Date: 23 July 2025
Revised Date: 27 September 2025
Accepted Date: 9 October 2025
Available Online: 10 October 2025

Figures(6)

The stereodivergent coupling via photoredox/transition metal catalysis has emerged as a powerful tool to construct diverse alkenes in both E and Z configurations. Despite well-established catalytic systems involving late transition metals, the early transition metal catalyzed stereodivergent synthesis of alkenes still remains underdeveloped. Herein in this work, a stereodivergent reductive C(sp²)-C(sp³) coupling between cycloketone oximes and vinyl halides has been achieved by tunable photoredox/Ti dual catalysis, providing a facile access to a broad scope of cyano-substituted (fluoro)alkenes with high efficiency and controlled E/Z selectivity. Several products exhibited promising antifungal activities.
- Photoredox/Ti dual catalysis,
- Stereodivergent,
- Reductive C(sp²)-C(sp³) coupling,
- Vinyl halides,
- E/Z Isomerization
1. [1]
  C. Dugave, L. Demange, Chem. Rev. 103 (2003) 2475–2532. doi: 10.1021/cr0104375
2. [2]
  C. Thirsk, A. Whiting, J. Chem. Soc., Perkin Trans. 1 (2002) 999–1023.
3. [3]
  T. Takeda, Modern Carbonyl Olefination: Methods and Applications, Wiley-VCH, 2004.
4. [4]
  S.W.M. Crossley, C. Obradors, R.M. Martinez, R.A. Shenvi, Chem. Rev. 116 (2016) 8912–9000. doi: 10.1021/acs.chemrev.6b00334
5. [5]
  O.M. Ogba, N.C. Warner, D.J. O'Leary, R.H. Grubbs, Chem. Soc. Rev. 47 (2018) 4510–4544. doi: 10.1039/c8cs00027a
6. [6]
  L. Jian, R.U. Zscherp, X. Shen, et al., J. Med. Chem. 66 (2023) 11940–11950. doi: 10.1021/acs.jmedchem.3c00549
7. [7]
  N. Vempala, S.V. Rao, A.J. Shree, B.S. Pradhan, Synthesis 48 (2016) 4167–4174. doi: 10.1055/s-0035-1562787
8. [8]
  Y. Asahina, K. Iwase, F. Iinuma, M. Hosaka, T. Ishizaki, J. Med. Chem. 48 (2005) 3194–3202. doi: 10.1021/jm0402061
9. [9]
  J.R. McCarthy, D.P. Matthews, D.M. Stemerick, et al., J. Am. Chem. Soc. 113 (1991) 7439–7440. doi: 10.1021/ja00019a061
10. [10]
  S.K. Pagire, T. Föll, O. Reiser, Acc. Chem. Res. 53 (2020) 782–791. doi: 10.1021/acs.accounts.9b00615
11. [11]
  Y. Gong, J. Hu, C. Qiu, H. Gong, Acc. Chem. Res. 57 (2024) 1149–1162. doi: 10.1021/acs.accounts.3c00810
12. [12]
  K. Singh, S.J. Staig, J.D. Weaver, J. Am. Chem. Soc. 136 (2014) 5275–5278. doi: 10.1021/ja5019749
13. [13]
  J.B. Metternich, R. Gilmour, J. Am. Chem. Soc. 137 (2015) 11254–11257. doi: 10.1021/jacs.5b07136
14. [14]
  J.B. Metternich, R. Gilmour, J. Am. Chem. Soc. 138 (2016) 1040–1045. doi: 10.1021/jacs.5b12081
15. [15]
  A. Singh, C.J. Fennel, J.D. Weaver, Chem. Sci. 7 (2016) 6796–6802. doi: 10.1039/C6SC02422J
16. [16]
  J.J. Molloy, J.B. Metternich, C.G. Daniliuc, A.J.B. Watson, R. Gilmour, Angew. Chem. Int. Ed. 57 (2018) 3168–3172. doi: 10.1002/anie.201800286
17. [17]
  J.J. Molloy, M. Schäfer, M. Wienhold, et al., Science 369 (2020) 302–306. doi: 10.1126/science.abb7235
18. [18]
  J. Xu, N. Liu, H. Lv, et al., Green Chem. 22 (2020) 2739–2743. doi: 10.1039/c9gc04303a
19. [19]
  X. Shen, C. Huang, X.A. Yuan, S. Yu, Angew. Chem. Int. Ed. 60 (2021) 9672–9679. doi: 10.1002/anie.202016941
20. [20]
  T. Neveselý, M. Wienhold, J.J. Molloy, R. Gilmour, Chem. Rev. 122 (2022) 2650–2694. doi: 10.1021/acs.chemrev.1c00324
21. [21]
  J. Xie, J. Yu, M. Rudolph, F. Rominger, A.S. Hashmi, Angew. Chem. Int. Ed. 55 (2016) 9416–9421. doi: 10.1002/anie.201602347
22. [22]
  X. Lu, Y. Wang, B. Zhang, et al., J. Am. Chem. Soc. 139 (2017) 12632–12637. doi: 10.1021/jacs.7b06469
23. [23]
  J. Li, Q. Lefebvre, H. Yang, Y. Zhao, H. Fu, Chem. Commun. 53 (2017) 10299–10302. doi: 10.1039/C7CC05758J
24. [24]
  H.W. Du, J. Sun, Q.S. Gao, et al., Org. Lett. 22 (2020) 1542–1546. doi: 10.1021/acs.orglett.0c00134
25. [25]
  M.Z. Lu, J. Goh, M. Maraswami, et al., Chem. Rev. 122 (2022) 17479–17646. doi: 10.1021/acs.chemrev.2c00032
26. [26]
  Z. Wang, Y. Sun, L.Y. Shen, et al., Org. Chem. Front. 9 (2022) 853–873. doi: 10.1039/D1QO01512E
27. [27]
  L.V. Hooker, J.S. Bandar, Angew. Chem. Int. Ed. 62 (2023) e202308880. doi: 10.1002/anie.202308880
28. [28]
  F. Wu, X. Li, J. Chang, D. Bai, Chin. Chem. Lett. 35 (2024) 109155. doi: 10.1016/j.cclet.2023.109155
29. [29]
  C. Liu, Y. Song, W. Ju, et al., Chin. Chem. Lett. 37 (2026) 111167. doi: 10.1016/j.cclet.2025.111167
30. [30]
  M. Nambo, K. Ghosh, J.C.H. Yim, et al., ACS Catal. 12 (2022) 9526–9532. doi: 10.1021/acscatal.2c02233
31. [31]
  S. Kumari, A.V. Carmona, A.K. Tiwari, P.C. Trippier, J. Med. Chem. 63 (2020) 12290–12358. doi: 10.1021/acs.jmedchem.0c00530
32. [32]
  E.M. Dauncey, S.P. Morcillo, J.J. Douglas, N.S. Sheikh, D. Leonori, Angew. Chem. Int. Ed. 57 (2018) 744–748. doi: 10.1002/anie.201710790
33. [33]
  X.Y. Yu, J.R. Chen, P.Z. Wang, et al., Angew. Chem. Int. Ed. 57 (2018) 738–743. doi: 10.1002/anie.201710618
34. [34]
  J. Chen, Y.J. Liang, P.Z. Wang, et al., J. Am. Chem. Soc. 143 (2021) 13382–13392. doi: 10.1021/jacs.1c06535
35. [35]
  D.M. Whalley, J. Seayad, M.F. Greaney, Angew. Chem. Int. Ed. 60 (2021) 22219–22223. doi: 10.1002/anie.202108240
36. [36]
  X.Y. Yu, J.R. Chen, W.J. Xiao, Chem. Rev. 121 (2021) 506–561. doi: 10.1021/acs.chemrev.0c00030
37. [37]
  K.A. Rykaczewski, E.R. Wearing, D.E. Blackmun, C.S. Schindler, Nat. Synth. 1 (2022) 24–36. doi: 10.1038/s44160-021-00007-y
38. [38]
  D.S. Bolotin, N.A. Bokach, M.Y. Demakova, V.Y. Kukushkin, Chem. Rev. 117 (2017) 13039–13122. doi: 10.1021/acs.chemrev.7b00264
39. [39]
  M. Manβen, L.L. Schafer, Chem. Soc. Rev. 49 (2020) 6947–6994. doi: 10.1039/d0cs00229a
40. [40]
  X. Wu, Y. Chang, S. Lin, Chem 8 (2022) 1805–1821. doi: 10.1016/j.chempr.2022.06.005
41. [41]
  Z. Zhang, R.B. Richrath, A. Gansäuer, ACS Catal. 9 (2019) 3208–3212. doi: 10.1021/acscatal.9b00787
42. [42]
  A. Gualandi, F. Calogero, M. Mazzarini, et al., ACS Catal. 10 (2020) 3857–3863. doi: 10.1021/acscatal.0c00348
43. [43]
  Z. Zhang, T. Hilche, D. Slak, et al., Angew. Chem. Int. Ed. 59 (2020) 9355–9359. doi: 10.1002/anie.202001508
44. [44]
  M. Parasram, B.J. Shields, O. Ahmad, T. Knauber, A.G. Doyle, ACS Catal. 10 (2020) 5821–5827. doi: 10.1021/acscatal.0c01199
45. [45]
  F. Li, S. Lin, Y. Chen, et al., Angew. Chem. Int. Ed. 60 (2021) 1561–1566. doi: 10.1002/anie.202010780
46. [46]
  W. Yuan, A. Qu, Y. Li, et al., Adv. Synth. Catal. 364 (2022) 3932–3940. doi: 10.1002/adsc.202200827
47. [47]
  H. Li, Y. Li, W. Yuan, et al., Green Synth. Catal. 5 (2024) 159–164. doi: 10.61935/acetr.2.1.2024.p159
48. [48]
  H. Zhang, X. Huang, Adv. Synth. Catal. 358 (2016) 3736–3742. doi: 10.1002/adsc.201600704
49. [49]
  J. Corpas, M.T. Quirós, P. Mauleón, R.G. Arrayás, J.C. Carretero, ACS Catal. 9 (2019) 10567–10574. doi: 10.1021/acscatal.9b02768
50. [50]
  C. Zhu, H. Yue, B. Maity, et al., Nat. Catal. 2 (2019) 678–687. doi: 10.1038/s41929-019-0311-x
51. [51]
  F. Song, F. Wang, L. Guo, et al., Angew. Chem. Int. Ed. 59 (2020) 177–181. doi: 10.1002/anie.201909543
52. [52]
  X. Li, M. Yuan, F. Chen, et al., Chem 9 (2023) 154–169. doi: 10.1016/j.chempr.2022.09.020
53. [53]
  J. Qin, Z. Zhang, Y. Lu, S. Zhu, L. Chu. Chem. Sci. 14 (2023) 12143–12151. doi: 10.1039/d3sc04645a
54. [54]
  F. Ye, S. Tong, W. Yuan, ACS Catal. 14 (2024) 9655–9661. doi: 10.1021/acscatal.4c02602
55. [55]
  M.M. Mastandrea, S. Cañellas, X. Caldentey, M.A. Pericàs, ACS Catal. 10 (2020) 6402–6408. doi: 10.1021/acscatal.0c01742
56. [56]
  H. Zhang, C. Huang, X.A. Yuan, S. Yu, J. Am. Chem. Soc. 144 (2022) 10958–10967. doi: 10.1021/jacs.2c04040
57. [57]
  H. Zhang, X. He, X.A. Yuan, S. Yu, ACS Catal. 13 (2023) 2857–2866. doi: 10.1021/acscatal.2c06183
58. [58]
  R.D. Connell, T.G. Lease, G.H. Ladouceur, M.H. Osterhout, Patent, US006048900A, 2000.
1. [1]
  Jialin Huang , Liying Fu , Zhanyong Tang , Xiaoqiang Ma , Xingda Zhao , Depeng Zhao . Cross-coupling of trifluoromethylarenes with alkynes C(sp)-H bonds and azoles C(sp²)-H bonds via photoredox/copper dual catalysis. Chinese Chemical Letters, 2025, 36(7): 110505-. doi: 10.1016/j.cclet.2024.110505
2. [2]
  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
3. [3]
  Xin-Han Wang , Ying Huang , Chun-Lin Zhang , Song Ye . γ-C(sp³)-H acylation of aliphatic amines enabled by cooperative photoredox NHC/Pd catalysis. Chinese Chemical Letters, 2026, 37(5): 111484-. doi: 10.1016/j.cclet.2025.111484
4. [4]
  Jun Jiang , Hui Dai , Tao Tu . Two vicinal C(sp³)-F bonds functionalization of perfluoroalkyl halides (PFAHs). Chinese Chemical Letters, 2025, 36(7): 111054-. doi: 10.1016/j.cclet.2025.111054
5. [5]
  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
6. [6]
  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
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]
  Yuemin Chen , Yunqi Wu , Guoao Wang , Feihu Cui , Haitao Tang , Yingming Pan . Electricity-driven enantioselective cross-dehydrogenative coupling of two C(sp³)-H bonds enabled by organocatalysis. Chinese Chemical Letters, 2024, 35(9): 109445-. doi: 10.1016/j.cclet.2023.109445
9. [9]
  Tong Li , Leping Pan , Yan Zhang , Jihu Su , Kai Li , Kuiliang Li , Hu Chen , Qi Sun , Zhiyong Wang . Electrochemical construction of 2,5-diaryloxazoles via N–H and C(sp³)-H functionalization. Chinese Chemical Letters, 2024, 35(4): 108897-. doi: 10.1016/j.cclet.2023.108897
10. [10]
  Zhiqian Chang , Xiaochun He , Xuemei Zhang , Zhong Lian . Stereoconvergent synthesis of chiral sulfonyl phthalide containing two chiral centers from Z/E mixed alkenes via copper catalysis. Chinese Chemical Letters, 2026, 37(5): 111405-. doi: 10.1016/j.cclet.2025.111405
11. [11]
  Xiu-Mei Xie , Hongyang Zhang , Shao-Xuan Gong , Hong-Xia Sun , Yu-Ting Liu , Xue-Ling Chen , Shuming Chen , Tian-Yu Gao , Wai-Yeung Wong , Zhen Zhang , Da-Gang Yu . Carbonylation of C(sp³)–H bonds with CO₂: Facile synthesis of 2,4-quinolinediones and related luminescent materials. Chinese Chemical Letters, 2026, 37(3): 112003-. doi: 10.1016/j.cclet.2025.112003
12. [12]
  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
13. [13]
  Jing Ren , Feng-Huan Du , Xiaowei Chen , Chi Zhang . Monofluoroiodane(Ⅲ) reagent mediated Wagner−Meerwein rearrangement fluorination: Construction of quaternary C(sp³)−F bond. Chinese Chemical Letters, 2026, 37(5): 111407-. doi: 10.1016/j.cclet.2025.111407
14. [14]
  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
15. [15]
  Da-Qiu Cui , Quan-Xin Li , Jia-Bo Huang , Ying-Qi Zhang , Xuan Wang , Shao-Fei Ni , Long-Wu Ye , Bo Zhou . Atroposelective transformation of vinyl cations by chiral Brønsted acid catalysis. Chinese Chemical Letters, 2026, 37(6): 111738-. doi: 10.1016/j.cclet.2025.111738
16. [16]
  Chongbei Wu , Benzhi Wang , Xuan Li , Jiaxuan Gu , Yihan Wu , Zhe Zhao , Pengfei Jia , Jizhou Jiang . Dual activation pathways based on OH-functionalized alk-Ti₃C₂ MXene/RuO_x boosting the hydrogen generation. Chinese Chemical Letters, 2025, 36(8): 111162-. doi: 10.1016/j.cclet.2025.111162
17. [17]
  Hong-Tao Ji , Yu-Han Lu , Yan-Ting Liu , Yu-Lin Huang , Jiang-Feng Tian , Feng Liu , Yan-Yan Zeng , Hai-Yan Yang , Yong-Hong Zhang , Wei-Min He . Nd@C₃N₄-photoredox/chlorine dual catalyzed synthesis and evaluation of antitumor activities of 4-alkylated sulfonyl ketimines. Chinese Chemical Letters, 2025, 36(2): 110568-. doi: 10.1016/j.cclet.2024.110568
18. [18]
  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
19. [19]
  Deng Pan , Chuan He , Genping Huang . Mechanism and origins of enantioselectivity of iridium-catalyzed atroposelective intermolecular C(sp²)-H silylation: A ligand-enabled axial chirality transfer strategy. Chinese Chemical Letters, 2026, 37(4): 111217-. doi: 10.1016/j.cclet.2025.111217
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(0)
Abstract views(16)
HTML views(0)

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

Stereodivergent reductive C(sp2)-C(sp3) coupling between cycloketone oximes and vinyl halides enabled by tunable photoredox/Ti dual catalysis

Metrics

通讯作者: 陈斌, bchen63@163.com

Stereodivergent reductive C(sp²)-C(sp³) coupling between cycloketone oximes and vinyl halides enabled by tunable photoredox/Ti dual catalysis