Citation: Shanxiang Liu, Jinxin Wang, Yuyong Ma, Xin Cao, Wei-Dong Zhang, Ang Li. Construction of alkyl-substituted 7-norbornenones through Diels−Alder cycloaddition of electron-deficient olefins and a cyclopentadienone derivative generated in situ[J]. Chinese Chemical Letters, ;2022, 33(4): 2041-2043. doi: 10.1016/j.cclet.2021.09.030 shu

Construction of alkyl-substituted 7-norbornenones through Diels−Alder cycloaddition of electron-deficient olefins and a cyclopentadienone derivative generated in situ

Shanxiang Liu ^{a, b, c} ,
Jinxin Wang ^{b, d, *,} ,
Yuyong Ma ^b ,
Xin Cao ^b ,
Wei-Dong Zhang ^{a, d, *,} ,
Ang Li ^{b, c, *,}

a.
School of Traditional Chinese Pharmacy, China Pharmaceutical University, Nanjing 211198, China
b.
State Key Laboratory of Bioorganic and Natural Products Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, University of Chinese Academy of Sciences, Shanghai 200032, China
c.
State Key Laboratory of Innovative Natural Medicine and Traditional Chinese Medicine Injections, Jiangxi Qingfeng Pharmaceutical Co. Ltd., Ganzhou 341000, China
d.
Department of Phytochemistry, School of Pharmacy, Second Military Medical University, Shanghai 200433, China

jxwang2013@126.com

wdzhangy@hotmail.com

ali@sioc.ac.cn

Received Date: 26 June 2021
Revised Date: 4 September 2021
Accepted Date: 7 September 2021
Available Online: 12 September 2021

Figures(3)

Dimeric sesquiterpenoids possessing densely substituted 7-norbornenone/7-norbornenol motifs pose a considerable challenge for chemical synthesis. From a strategic perspective, one could envision intermolecular Diels−Alder cycloaddition as a straightforward method for assembling alkyl-substituted 7-norbornenones. However, this approach is hindered by lability of the required dienes, namely alkyl-substituted cyclopentadienones. Here we report a one-pot protocol for construction of alkyl-substituted 7-norbornenones from electron-deficient olefins and a cyclopentenone derivative. DDQ was found to be an effective oxidant for generating a cyclopentadienone intermediate in situ from the enone. A series of sterically congested 7-norbornenone-containing polycyclic compounds were prepared by using this protocol.
- 7-Norbornenone,
- Alkyl-substituted cyclopentadienone,
- Diels−Alder cycloaddition,
- Dimeric sesquiterpenoid
1. [1]
  S.G. Liao, J.M. Yue, Prog. Chem. Org. Nat. Prod. 101 (2016) 1–112.
2. [2]
  Z.J. Zhan, Y.M. Ying, L.F. Ma, W.G. Shan, Nat. Prod. Rep. 28 (2011) 594–629. doi: 10.1039/c0np00050g
3. [3]
  Y.L. Zhang, X.W. Zhou, X.B. Wang, et al., Org. Lett. 19 (2017) 3013–3016. doi: 10.1021/acs.orglett.7b01276
4. [4]
  J.J. Qin, H.Z. Jin, J.J. Fu, et al., Bioorg. Med. Chem. Lett. 19 (2009) 710–713.
5. [5]
  M.A. Ogliaruswo, M.G. Romanelli, E.I. Becker, Chem. Rev. 65 (1965) 261–367.
6. [6]
  C.J. Walsh, B.K. Mandal, J. Org. Chem. 64 (1999) 6102–6105.
7. [7]
  T. Shibata, K. Yamashita, H. Ishida, K. Takagi, Org. Lett. 3 (2001) 1217–1219.
8. [8]
  J.E. Moore, M. York, J.P.A. Harrity, Synlett 2005 (2005) 860–862.
9. [9]
  P.A. Wender, T.J. Paxton, T.J. Williams, J. Am. Chem. Soc. 128 (2006) 14814–14815. doi: 10.1021/ja065868p
10. [10]
  S. Murakami, T. Sonehara, K. Iwakami, H. Tsuji, M. Kawatsura, Tetrahedron Lett. 60 (2019) 598–601.
11. [11]
  C.F.H. Allen, J.A. VanAllan, J. Am. Chem. Soc. 72 (1950) 5165–5167. doi: 10.1021/ja01167a102
12. [12]
  E.W. Garbisch, Jr., R.F. Sprecher, J. Am. Chem. Soc. 91 (1969) 6785–6800. doi: 10.1021/ja01052a042
13. [13]
  P.E. Eaton, R.A. Hudson, J. Am. Chem. Soc. 87 (1965) 2769–2711. doi: 10.1021/ja01090a052
14. [14]
  P.E. Eaton, C. Giordano, U. Vogel, J. Org. Chem. 41 (1976) 2236–2238. doi: 10.1021/jo00875a002
15. [15]
  I. Fleming, J.P. Michael, J. Chem. Soc., Perkin Trans. 1 (1981) 1549–1556.
16. [16]
  P. Preethalayam, K.S. Krishnan, S. Thulasi, et al., Chem. Rev. 117 (2017) 3930–3989. doi: 10.1021/acs.chemrev.6b00210
17. [17]
  M.A. Battiste, M. Visnick, Tetrahedron Lett. 19 (1978) 4771–4774.
18. [18]
  J. Deng, B. Zhu, Z. Lu, H. Yu, A. Li, J. Am. Chem. Soc. 134 (2012) 920–923. doi: 10.1021/ja211444m
19. [19]
  J. Deng, S. Zhou, W. Zhang, et al., J. Am. Chem. Soc. 136 (2014) 8185–8188. doi: 10.1021/ja503972p
20. [20]
  M. Yang, J. Li, A. Li, Nat. Commun. 6 (2015) 6445.
21. [21]
  W. Zhang, M. Ding, J. Li, et al., J. Am. Chem. Soc. 140 (2018) 4227–4231. doi: 10.1021/jacs.8b01681
22. [22]
  S. Zhou, R. Guo, P. Yang, A. Li, J. Am. Chem. Soc. 140 (2018) 9025–9029. doi: 10.1021/jacs.8b03712
23. [23]
  S. Zhou, K. Xia, X. Leng, A. Li, J. Am. Chem. Soc. 141 (2019) 13718–13723. doi: 10.1021/jacs.9b05818
24. [24]
  S. Dong, E. Hamel, R. Bai, et al., Angew. Chem. Int. Ed. 48 (2009) 1494–1497. doi: 10.1002/anie.200805486
25. [25]
  D. Walker, J.D. Hiebert, Chem. Rev. 67 (1967) 153–195. doi: 10.1021/cr60246a002
26. [26]
  X. Xiong, D. Zhang, J. Li, et al., Chem. Asian J. 10 (2015) 869–872. doi: 10.1002/asia.201403312
1. [1]
  Deli Chen , Jiawen Li , Xudong Xu , Zhaocui Sun , Yun Yang , Minghui Xu , Hanqiao Liang , Junshan Yang , Hui Meng , Guoxu Ma , Jianhe Wei . Plant-microbial interactions inspired the discovery of novel sesquiterpenoid dimeric skeletons of hidden natural products from Hibiscus tiliaceus. Chinese Chemical Letters, 2024, 35(10): 109451-. doi: 10.1016/j.cclet.2023.109451
2. [2]
  Yu-Hang Miao , Zheng-Xu Zhang , Xu-Yi Huang , Yuan-Zhao Hua , Shi-Kun Jia , Xiao Xiao , Min-Can Wang , Li-Ping Xu , Guang-Jian Mei . Catalytic asymmetric dearomative azo-Diels–Alder reaction of 2-vinlyindoles. Chinese Chemical Letters, 2024, 35(4): 108830-. doi: 10.1016/j.cclet.2023.108830
3. [3]
  Fangqing Zhang , Yu Wang , Zhenda Tan , Yangbin Liu , Lijuan Song , Xiaoming Feng . Catalytic asymmetric inverse-electron-demand Diels–Alder reaction of 2-pyrones with aryl enol ethers. Chinese Chemical Letters, 2025, 36(7): 110581-. doi: 10.1016/j.cclet.2024.110581
4. [4]
  Ling Fan , Meili Pang , Yeyun Zhang , Yanmei Wang , Zhenfeng Shang . Quantum Chemistry Calculation Research on the Diels-Alder Reaction of Anthracene and Maleic Anhydride: Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 133-139. doi: 10.3866/PKU.DXHX202309024
5. [5]
  Yiying Yang , Dongju Zhang . Elucidating the Concepts of Thermodynamic Control and Kinetic Control in Chemical Reactions through Theoretical Chemistry Calculations: A Computational Chemistry Experiment on the Diels-Alder Reaction. University Chemistry, 2024, 39(3): 327-335. doi: 10.3866/PKU.DXHX202309074
6. [6]
  Wen-Rui Li , Ru-Bing Wang , Huiqiang Wang , Jin-Yao Yong , Yu-Huan Li , Shi-Shan Yu , Shuang-Gang Ma . Ring-reorganization strategy for asymmetric synthesis of sesquiterpenoid illihenin A and its antiviral activity evaluation. Chinese Chemical Letters, 2025, 36(11): 110945-. doi: 10.1016/j.cclet.2025.110945
7. [7]
  Ling-Hao Zhao , Hai-Wei Yan , Jian-Shuang Jiang , Xu Zhang , Xiang Yuan , Ya-Nan Yang , Pei-Cheng Zhang . Effective assignment of positional isomers in dimeric shikonin and its analogs by ¹H NMR spectroscopy. Chinese Chemical Letters, 2024, 35(5): 108863-. doi: 10.1016/j.cclet.2023.108863
8. [8]
  Hongyuan Sha , Dongling Yang , Yanran Shang , Zujian Wang , Rongbing Su , Chao He , Xiaoming Yang , Xifa Long . Trithionic guanidine: A novel semi-organic short-wave ultraviolet nonlinear optical sulfate with dimeric heteroleptic tetrahedra. Chinese Chemical Letters, 2025, 36(4): 109730-. doi: 10.1016/j.cclet.2024.109730
9. [9]
  Qian-Cheng Luo , Xia-Li Ding , Wen-Jie Xu , Yuan-Qi Zhai , Yan-Zhen Zheng . Equatorial aminopyridine ligands stabilize an unusual straightly bridging mode in dimeric dysprosium(Ⅲ) single-molecule magnets. Chinese Chemical Letters, 2025, 36(9): 110304-. doi: 10.1016/j.cclet.2024.110304
10. [10]
  Min Yan , Zihao Ye , Ping Lu . Catalyst-free, visible-light-induced [2π + 2σ] cycloaddition towards azabicyclohexanes. Chinese Chemical Letters, 2025, 36(6): 110540-. doi: 10.1016/j.cclet.2024.110540
11. [11]
  Meixin Wang , Yizhi Zhang , Shanshan Liu , Xiao Shen . Synthesis of rigidified cyclohexanes enabled by visible-light-induced trifluoroacetylsilane-mediated [2 + 2] cycloaddition of cyclopropenes. Chinese Chemical Letters, 2025, 36(8): 110758-. doi: 10.1016/j.cclet.2024.110758
12. [12]
  Ruolin CHENG , Yue WANG , Fei YANG , Huagen LIANG , Shijian LU . Application of metal-organic frameworks (MOFs) in photocatalytic CO₂ cycloaddition reaction: A mini review. Chinese Journal of Inorganic Chemistry, 2025, 41(12): 2429-2440. doi: 10.11862/CJIC.20250242
13. [13]
  Qihang Wu , Hui Wen , Wenhai Lin , Tingting Sun , Zhigang Xie . Alkyl chain engineering of boron dipyrromethenes for efficient photodynamic antibacterial treatment. Chinese Chemical Letters, 2024, 35(12): 109692-. doi: 10.1016/j.cclet.2024.109692
14. [14]
  Hefei Yang , Le-Cheng Wang , Xiao-Feng Wu . Sustainable carbonylative transformation of alkyl iodides to amides via crosslinking of EDA and XAT. Chinese Chemical Letters, 2025, 36(9): 110843-. doi: 10.1016/j.cclet.2025.110843
15. [15]
  . . University Chemistry, 2024, 39(7): 0-0.
16. [16]
  Yan Guo , Hongtao Bian , Le Yu , Jiani Ma , Yu Fang . Photochemical reaction mechanism of benzophenone protected guanosine at N7 position. Chinese Chemical Letters, 2025, 36(3): 109971-. doi: 10.1016/j.cclet.2024.109971
17. [17]
  . . University Chemistry, 2025, 40(7): 0-0.
18. [18]
  . 第41卷第7期封面和目次. Acta Physico-Chimica Sinica, 2025, 41(7): -.
19. [19]
  Wenxiong Yu , Chenyu Yang , Xian Feng , Chengshuo Shen . Scholl cyclization of [6]helicenes into negatively curved hexa[7]circulenes. Chinese Chemical Letters, 2025, 36(11): 110939-. doi: 10.1016/j.cclet.2025.110939
20. [20]
  Ruowen Liang , Chao Zhang , Guiyang Yan . Enhancing CO2 cycloaddition through ligand functionalization: A case study of UiO-66 metal-organic frameworks. Chinese Journal of Structural Chemistry, 2024, 43(2): 100211-100211. doi: 10.1016/j.cjsc.2023.100211

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(1304)
HTML views(150)

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