Citation: Ze-Hong Zheng, Mu-Qiu Chen, Jin Zhou, Jie Wang, Yan-Rong Wei, Cheng Peng, Gu Zhan, Qian-Qian Yang, Bo Han. Diverse synthesis of bridged bicyclo[3.2.1]octa-2,6-diene and tricyclo[3.2.1.0^2,7]oct-3-ene frameworks via stepwise cascade reactions[J]. Chinese Chemical Letters, ;2025, 36(12): 111202. doi: 10.1016/j.cclet.2025.111202 shu

Diverse synthesis of bridged bicyclo[3.2.1]octa-2,6-diene and tricyclo[3.2.1.0^2,7]oct-3-ene frameworks via stepwise cascade reactions

State Key Laboratory of Southwestern Chinese Medicine Resources, School of Pharmacy, Chengdu University of Traditional Chinese Medicine, Chengdu 611137, China

yangqq@cdutcm.edu.cn

hanbo@cdutcm.edu.cn

Received Date: 22 December 2024
Revised Date: 31 March 2025
Accepted Date: 11 April 2025
Available Online: 12 April 2025

Figures(5)

Strained bridged rings bicyclo[3.2.1]octane and tricyclo[3.2.1.0^2,7]octane are prevalent in natural products known for their significant biological activities. However, strategies for efficiently synthesizing these complex frameworks from simple starting materials via de novo synthesis remain underexplored. This article presents an efficient strategy that combines phosphine catalysis and photocatalysis to execute a stepwise tandem reaction involving allenoates and α-cyano cinnamaldehydes, including [3 + 2] cyclization, [5 + 2] cyclization, acyl transfer, and decarboxylation reactions, synthesizing a series of functional bicyclo[3.2.1]octa-2,6-diene and tricyclo[3.2.1.0^2,7]oct–3-ene skeleton derivatives with excellent chemoselectivity demonstrated throughout the process. Meanwhile, the reaction can also be performed via a one-pot, scalable phosphine/photocatalytic cascade process, efficiently yielding the bridged products which can serve as versatile intermediates for further applications.
1. [1]
  C.W. Murray, D.C. Rees, Nat. Chem. 1 (2009) 187–192. doi: 10.1038/nchem.217
2. [2]
  Y. Wang, P. Tang, W. Tu, et al., Chin. Chem. Lett. 36 (2025) 109955. doi: 10.1016/j.cclet.2024.109955
3. [3]
  J. Du, J. Guo, D. Kang, et al., Chin. Chem. Lett. 31 (2020) 1695–1708. doi: 10.1016/j.cclet.2020.03.028
4. [4]
  A. Dai, Z. Zheng, L. Duan, et al., Chin. Chem. Lett. 35 (2024) 110462.
5. [5]
  E.A. Crane, K. Gademann, Angew. Chem. Int. Ed. 55 (2016) 3882–3902. doi: 10.1002/anie.201505863
6. [6]
  J. Shearer, J.L. Castro, A.D. G Lawson, et al., J. Med. Chem. 65 (2022) 8699–8712. doi: 10.1021/acs.jmedchem.2c00473
7. [7]
  M. Wu, K. Ren, C. Zou, et al., Chin. Chem. Lett. 35 (2024) 110213.
8. [8]
  Q. Zhang, Y. Kuang, L. Chang, et al., Chin. Chem. Lett. 35 (2024) 108338. doi: 10.1016/j.cclet.2023.108338
9. [9]
  T. Mori, R. Zhai, R. Ushimaru, et al., Nat. Commun. 12 (2021) 4417. doi: 10.1038/s41467-021-24685-6
10. [10]
  W.Y. Liu, X.X. Lei, W.J. Wang, et al., Chin. Chem. Lett. 35 (2024) 110478.
11. [11]
  F. Zhang, Y. Wang, Z. Tan, et al., Chin. Chem. Lett. 35 (2024) 110581.
12. [12]
  S. Levin, R.R. Nani, S.E. Reisman, Org. Lett. 12 (2010) 780–783. doi: 10.1021/ol902848k
13. [13]
  Y.J. Hu, C.C. Gu, X.F. Wang, et al., J. Am. Chem. Soc. 143 (2021) 17862–17870. doi: 10.1021/jacs.1c09637
14. [14]
  P. Chen, L. Liang, Y. Zhu, et al., Chin. Chem. Lett. 35 (2024) 109229. doi: 10.1016/j.cclet.2023.109229
15. [15]
  L.X. Li, L. Min, T.B. Yao, et al., J. Am. Chem. Soc. 144 (2022) 18823–18828. doi: 10.1021/jacs.2c09548
16. [16]
  K.R. Owens, S.V. McCowen, K.A. Blackford, et al., J. Am. Chem. Soc. 141 (2019) 13713–13717. doi: 10.1021/jacs.9b05815
17. [17]
  S.J. Davidson, D. Barker, Angew. Chem. Int. Ed. 56 (2017) 9483–9486. doi: 10.1002/anie.201705575
18. [18]
  L. Min, X. Liu, C.C. Li, Acc. Chem. Res. 53 (2020) 703–718. doi: 10.1021/acs.accounts.9b00640
19. [19]
  J. Liu, X. Liu, J. Wu, C.C. Li, Chem 6 (2020) 579–615. doi: 10.1016/j.chempr.2019.12.027
20. [20]
  K. Nagaraju, D. Ni, D. Ma, Angew. Chem. Int. Ed. 59 (2020) 22039–22042. doi: 10.1002/anie.202011093
21. [21]
  Z. Lu, H. Li, M. Bian, A. Li, J. Am. Chem. Soc. 137 (2015) 13764–13767. doi: 10.1021/jacs.5b09198
22. [22]
  Z. Zhou, A.X. Gao, S.A. Snyder, J. Am. Chem. Soc. 141 (2019) 7715–7720. doi: 10.1021/jacs.9b03248
23. [23]
  L. Li, Z.L. Li, F.L. Wang, et al., Nat. Commun. 7 (2016) 13852. doi: 10.1038/ncomms13852
24. [24]
  T.C. Coombs, Y. Zhang, E.C. Garnier-Amblard, L.S. Liebeskind, J. Am. Chem. Soc. 131 (2009) 876–877. doi: 10.1021/ja808533z
25. [25]
  J.E. DeLorbe, D. Horne, R. Jove, et al., J. Am. Chem. Soc. 135 (2013) 4117–4128. doi: 10.1021/ja400315y
26. [26]
  J.E. DeLorbe, S.Y. Jabri, S.M. Mennen, et al., J. Am. Chem. Soc. 133 (2011) 6549–6552. doi: 10.1021/ja201789v
27. [27]
  Q. Tan, Z. Yang, D. Jiang, et al., Angew. Chem. Int. Ed. 58 (2019) 6420–6424. doi: 10.1002/anie.201902155
28. [28]
  M.J.R. Richter, M. Schneider, M. Brandstätter, et al., J. Am. Chem. Soc. 140 (2018) 16704–16710. doi: 10.1021/jacs.8b09685
29. [29]
  L.A. Wein, K. Wurst, P. Angyal, et al., J. Am. Chem. Soc. 141 (2019) 19589–19593. doi: 10.1021/jacs.9b11646
30. [30]
  C. Li, D. Lee, T.N. Graf, et al., Org. Lett. 7 (2005) 5709–5712. doi: 10.1021/ol052498l
31. [31]
  Y. Aoyagi, A. Yamazaki, C. Nakatsugawa, et al., Org. Lett. 10 (2008) 4429–4432. doi: 10.1021/ol801620u
32. [32]
  C.C. Tseng, H. Ding, A. Li, et al., Org. Lett. 13 (2011) 4410–4413. doi: 10.1021/ol201748x
33. [33]
  S. Levin, R.R. Nani, S.E. Reisman, J. Am. Chem. Soc. 133 (2010) 774–776.
34. [34]
  T.T. Song, Y.K. Mei, Y. Liu, et al., Angew. Chem. Int. Ed. 63 (2024) e202314304. doi: 10.1002/anie.202314304
35. [35]
  J.M. Anderson, N.D. Measom, J.A. Murphy, D.L. Poole, Angew. Chem. Int. Ed. 60 (2021) 24754–24769. doi: 10.1002/anie.202106352
36. [36]
  X. Liu, J. Liu, J. Wu, et al., J. Am. Chem. Soc. 141 (2019) 2872–2877. doi: 10.1021/jacs.8b12647
37. [37]
  W. Zhang, L. Li, C.C. Li, Chem. Soc. Rev. 50 (2021) 9430–9442. doi: 10.1039/d0cs01471k
38. [38]
  K. Gao, J. Hu, H. Ding, Acc. Chem. Res. 54 (2021) 875–889. doi: 10.1021/acs.accounts.0c00798
39. [39]
  M.H. Filippini, J. Rodriguez, Chem. Rev. 99 (1999) 27–76. doi: 10.1021/cr970029u
40. [40]
  M. Presset, Y. Coquerel, J. Rodriguez, Chem. Rev. 113 (2012) 525–595.
41. [41]
  J. Zhuo, C. Zhu, J. Wu, et al., J. Am. Chem. Soc. 144 (2021) 99–105.
42. [42]
  W. Adam, O. De Lucchi, K. Peters, et al., J. Am. Chem. Soc. 104 (1982) 161–166. doi: 10.1021/ja00365a029
43. [43]
  Z. Yuan, Z. Feng, Y. Zeng, et al., Angew. Chem. Int. Ed. 58 (2019) 2884–2888. doi: 10.1002/anie.201900059
44. [44]
  B. Chen, Y. Zhang, R. Wu, et al., ACS Catal. 9 (2019) 11788–11793. doi: 10.1021/acscatal.9b04183
45. [45]
  Z. Yuan, Y. Zeng, Z. Feng, et al., Nat. Commun. 11 (2020) 2544. doi: 10.1038/s41467-020-16221-9
46. [46]
  I. Škorić, M. Šmehil, Ž. Marinić, et al, J. Chem. Phys. 207 (2009) 190–196.
47. [47]
  D. Skropeta, R.W. Rickards, Tetrahedron Lett. 48 (2007) 3281–3284. doi: 10.1016/j.tetlet.2007.03.011
48. [48]
  M. Ramirez, V. Vece, S. Hanessian, K.N. Houk, J. Org. Chem. 86 (2021) 17955–17964. doi: 10.1021/acs.joc.1c02296
49. [49]
  S. Zhu, Z. Guo, Z. Huang, H. Jiang, Chem. Eur. J. 20 (2014) 2425–2430. doi: 10.1002/chem.201304839
50. [50]
  X. Wang, Z. Han, Z. Wang, K. Ding, Acc. Chem. Res. 54 (2021) 668–684. doi: 10.1021/acs.accounts.0c00697
51. [51]
  X. Fan, Y. He, X. Zhang, Chem. Rec. 16 (2016) 1635–1646. doi: 10.1002/tcr.201500301
52. [52]
  X. Lu, C. Zhang, Z. Xu, Acc. Chem. Res. 34 (2001) 535–544. doi: 10.1021/ar000253x
53. [53]
  L.W. Ye, J. Zhou, Y. Tang, Chem. Soc. Rev. 37 (2008) 1140–1152. doi: 10.1039/b717758e
54. [54]
  H. Ni, W.L. Chan, Y. Lu, Chem. Rev. 118 (2018) 9344–9411. doi: 10.1021/acs.chemrev.8b00261
55. [55]
  H. Guo, Y.C. Fan, Z. Sun, et al., Chem. Rev. 118 (2018) 10049–10293. doi: 10.1021/acs.chemrev.8b00081
56. [56]
  X. Li, J. Liao, X. Zhuo, et al., Green Synth. Catal. 4 (2023) 54–57.
57. [57]
  Y. Li, M. Dai, Angew. Chem. Int. Ed. 56 (2017) 11624–11627. doi: 10.1002/anie.201706845
58. [58]
  L.Z. Li, Y.R. Huang, Z.X. Xu, et al., J. Am. Chem. Soc. 146 (2024) 24782–24787. doi: 10.1021/jacs.4c09384
59. [59]
  C.H. Liu, Z.X. Yu, Angew. Chem. Int. Ed. 56 (2017) 8667–8671. doi: 10.1002/anie.201702288
60. [60]
  Q.Q. Yang, C. Chen, D. Yao, et al., Angew. Chem. Int. Ed. 63 (2023) e202312663.
61. [61]
  C. Chen, J. Zhou, J. Jiang, et al., Chin. Chem. Lett. 35 (2024) 108295. doi: 10.1016/j.cclet.2023.108295
62. [62]
  Q.Q. Yang, S.J. Liu, W. Huang, et al., Research 7 (2024) 0410. doi: 10.34133/research.0410
63. [63]
  C. Yuan, H. Tan, X.F. Jiang, et al., Asian J. Org. Chem. 8 (2019) 1893–1902. doi: 10.1002/ajoc.201900393
64. [64]
  Z. Xu, X.J. Lu, Org. Chem. 63 (1998) 5031–5041. doi: 10.1021/jo9723063
65. [65]
  X. Creary, M.A. Butchko, J. Am. Chem. Soc. 13 (2001) 1569–1578.
66. [66]
  H.E. Zimmerman, R.W. Binkley, R.S. Givens, M. Sherwin, J. Am. Chem. Soc. 89 (1967) 3932–3933. doi: 10.1021/ja00991a064
67. [67]
  Y. Zheng, Q.X. Dong, S.Y. Wen, et al., J. Am. Chem. Soc. 146 (2024) 18210– 18217. doi: 10.1021/jacs.4c04370
68. [68]
  Z.C. He, S.K. Mellerup, L. Liu, et al., Angew. Chem. Int. Ed. 58 (2019) 6683–6687. doi: 10.1002/anie.201902231
69. [69]
  P. Milbeo, J. Martinez, M. Amblard, et al., Acc. Chem. Res. 54 (2021) 685–696. doi: 10.1021/acs.accounts.0c00680
1. [1]
  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
2. [2]
  Xuling Pan , Wei Cai , You Huang . Recent advances in phosphine-mediated sequential annulations. Chinese Chemical Letters, 2025, 36(5): 110628-. doi: 10.1016/j.cclet.2024.110628
3. [3]
  Chenxi Shang , Boxuan Lu , Chongbei Wu , Shuqing Zhou , Luyan Shi , Tayirjan Taylor Isimjan , Xiulin Yang . Inducing electronic rearrangement through Co₃B-Mo₂B₅ catalysts: Efficient dual-function catalysis for NaBH₄ hydrolysis and 4-nitrophenol reduction. Chinese Chemical Letters, 2025, 36(9): 111152-. doi: 10.1016/j.cclet.2025.111152
4. [4]
  Junhua Wang , Xin Lian , Xichuan Cao , Qiao Zhao , Baiyan Li , Xian-He Bu . Dual polarization strategy to enhance CH₄ uptake in covalent organic frameworks for coal-bed methane purification. Chinese Chemical Letters, 2024, 35(8): 109180-. doi: 10.1016/j.cclet.2023.109180
5. [5]
  Jieshuai Xiao , Yuan Zheng , Yue Zhao , Zhuangzhi Shi , Minyan Wang . Asymmetric Nozaki-Hiyama-Kishi (NHK)-type reaction of isatins with aromatic iodides by cobalt catalysis. Chinese Chemical Letters, 2025, 36(5): 110243-. doi: 10.1016/j.cclet.2024.110243
6. [6]
  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
7. [7]
  Rong-Nan Yi , Wei-Min He . Photocatalytic Minisci-type multicomponent reaction for the synthesis of 1-(halo)alkyl-3-heteroaryl bicyclo[1.1.1]pentanes. Chinese Chemical Letters, 2024, 35(10): 110115-. doi: 10.1016/j.cclet.2024.110115
8. [8]
  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
9. [9]
  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
10. [10]
  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
11. [11]
  Weichen WANG , Chunhua GONG , Junyong ZHANG , Yanfeng BI , Hao XU , Jingli XIE . Construction of two metal-organic frameworks by rigid bis(triazole) and carboxylate mixed-ligands and their catalytic properties for CO₂ cycloaddition reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1377-1386. doi: 10.11862/CJIC.20230415
12. [12]
  Quanyou Guo , Yue Yang , Tingting Hu , Hongqi Chu , Lijun Liao , Xuepeng Wang , Zhenzi Li , Liping Guo , Wei Zhou . Regulating local electron transfer environment of covalent triazine frameworks through F, N co-modification towards optimized oxygen reduction reaction. Chinese Chemical Letters, 2025, 36(1): 110235-. doi: 10.1016/j.cclet.2024.110235
13. [13]
  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
14. [14]
  Yi Herng Chan , Zhe Phak Chan , Serene Sow Mun Lock , Chung Loong Yiin , Shin Ying Foong , Mee Kee Wong , Muhammad Anwar Ishak , Ven Chian Quek , Shengbo Ge , Su Shiung Lam . Thermal pyrolysis conversion of methane to hydrogen (H₂): A review on process parameters, reaction kinetics and techno-economic analysis. Chinese Chemical Letters, 2024, 35(8): 109329-. doi: 10.1016/j.cclet.2023.109329
15. [15]
  Qi Zhang , Bin Han , Yucheng Jin , Mingrun Li , Enhui Zhang , Jianzhuang Jiang . 2D and 3D phthalocyanine covalent organic frameworks for electrocatalytic carbon dioxide reduction. Chinese Chemical Letters, 2025, 36(9): 110330-. doi: 10.1016/j.cclet.2024.110330
16. [16]
  Ning LI , Siyu DU , Xueyi WANG , Hui YANG , Tao ZHOU , Zhimin GUAN , Peng FEI , Hongfang MA , Shang JIANG . Preparation and efficient catalysis for olefins epoxidation of a polyoxovanadate-based hybrid. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 799-808. doi: 10.11862/CJIC.20230372
17. [17]
  Uttam Pandurang Patil . Porous carbon catalysis in sustainable synthesis of functional heterocycles: An overview. Chinese Chemical Letters, 2024, 35(8): 109472-. doi: 10.1016/j.cclet.2023.109472
18. [18]
  Liliang Chu , Xiaoyan Zhang , Jianing Li , Xuelei Deng , Miao Wu , Ya Cheng , Weiping Zhu , Xuhong Qian , Yunpeng Bai . Continuous-flow synthesis of polysubstituted γ-butyrolactones via enzymatic cascade catalysis. Chinese Chemical Letters, 2024, 35(4): 108896-. doi: 10.1016/j.cclet.2023.108896
19. [19]
  Hao-Cong Li , Ming Zhang , Qiyan Lv , Kai Sun , Xiao-Lan Chen , Lingbo Qu , Bing Yu . Homogeneous catalysis and heterogeneous separation: Ionic liquids as recyclable photocatalysts for hydroacylation of olefins. Chinese Chemical Letters, 2025, 36(2): 110579-. doi: 10.1016/j.cclet.2024.110579
20. [20]
  Jing Guo , Jianzhong Ma , Junli Liu , Guanjie Huang , Xiaoting Zhou , Francesco Parrino , Riccardo Ceccato , Leonardo Palmisano , Boon-Junn Ng , Lutfi Kurnianditia Putri , Huaxing Li , Rongjie Li , Gang Liu , Yang Wang , Nikolay Kornienko , Shan-Shan Zhu , Zhenwei Zhang , Xiaoming Liu , Nur Atika Nikma Dahlan , Siang-Piao Chai , Jianmin Ma . Two-dimensional nanomaterials for environmental catalysis roadmap towards 2030. Chinese Chemical Letters, 2025, 36(9): 110988-. doi: 10.1016/j.cclet.2025.110988

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(17)
HTML views(6)

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

Diverse synthesis of bridged bicyclo[3.2.1]octa-2,6-diene and tricyclo[3.2.1.02,7]oct-3-ene frameworks via stepwise cascade reactions

Metrics

通讯作者: 陈斌, bchen63@163.com

Diverse synthesis of bridged bicyclo[3.2.1]octa-2,6-diene and tricyclo[3.2.1.0^2,7]oct-3-ene frameworks via stepwise cascade reactions