Citation: Zhu Xinju, Niu Junlong, Zhao Xuemei, Hao Xinqi, Song Maoping. Synthesis of Chiral Bis(imidazoline) Ligands with Biphenyl Backbone and Their Application in the Asymmetric Cyclopropanation Reaction[J]. Chinese Journal of Organic Chemistry, ;2018, 38(1): 118-123. doi: 10.6023/cjoc201708037 shu

Synthesis of Chiral Bis(imidazoline) Ligands with Biphenyl Backbone and Their Application in the Asymmetric Cyclopropanation Reaction

College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001

Corresponding author: Hao Xinqi, xqhao@zzu.edu.cn Song Maoping, mpsong@zzu.edu.cn
Received Date: 19 August 2017
Revised Date: 8 November 2017
Available Online: 17 January 2017
Fund Project: the National Natural Science Foundation of Chin 21672192the National Natural Science Foundation of Chin 21528201the China Postdoctoral Science Foundation 2016M602254Project supported by the National Natural Science Foundation of China (Nos. 21528201, 21672192) and the China Postdoctoral Science Foundation (No. 2016M602254)

Figures(4)

A serial of biphenyl bisimidazolines containing both axial and central chirality have been synthesized for the first time. Compared with common method, Ullmann coupling methodology exhibited superior performance expecially for t-Bu substituted ligands. The obtained ligands were further applied in the Cu-catalyzed asymmetric cyclopropanation.
- imidazoline,
- axial chirality,
- central chirality,
- asymmetric cyclopropanation
1. [1]
  (a) Farina, V. ; Reeves, J. T. ; Senanayake, C. H. ; Song, J. J. Chem. Rev. 2006, 106, 2734.
  (b) Blaser, H. U. Adv. Synth. Catal. 2002, 344, 17.
2. [2]
  For review, see:(a) Rechavi, D.; Lemaire, M. Chem. Rev. 2002, 102, 3467.
  (b) McManus, H. A.; Guiry, P. J. Chem. Rev. 2004, 104, 4151.
  (c) Desimoni, G.; Faita, G.; J rgensen, K. A. Chem. Rev. 2006, 106, 3561.
  (d) Hargaden, G. C.; Guiry, P. J. Chem. Rev. 2009, 109, 2505.
  (e) Desimoni, G.; Faita, G.; J rgensen, K. A. Chem. Rev. 2011, 111, PR284.
3. [3]
  (a) Knowles, W. S.; Sabacky, M. J.; Vineyard, B. D.; Weinkauff, D. J. J. Am. Chem. Soc. 1975, 97, 2567.
  (b) Evans, D. A.; Faul, M. M.; Bilodeau, M. T.; Anderson, B. A.; Barnes, D. M. J. Am. Chem. Soc. 1993, 115, 5328.
4. [4]
  (a) Zhang, W. ; Hirao, T. ; Ikeda, I. Tetrahedron Lett. 1996, 37, 4545.
  (b) Schaarschmidt, D. ; Lang, H. Organometallics 2013, 32, 5668.
5. [5]
  (a) Nelson, T. D. ; Meyers, A. I. J. Org. Chem. 1994, 59, 2655.
  (b) Gant, T. G. ; Noe, M. C. ; Corey, E. J. Tetrahedron Lett. 1995, 36, 8745.
  (c) Meyers, A. I. ; McKennon, M. J. Tetrahedron Lett. 1995, 36, 5869.
6. [6]
  (a) Uozumi, Y. ; Kyota, H. ; Kishi, E. ; Kitayama, K. ; Hayashi, T. Tetrahedron: Asymmetry 1996, 7, 1603.
  (b) Andrus, M. B. ; Asgari, D. ; Sclafani, J. A. J. Org. Chem. 1997, 62, 9365.
  (c) Meyers, A. I. ; Price, A. J. Org. Chem. 1998, 63, 412.
  (d) Andrus, M. B. ; Asgari, D. Tetrahedron 2000, 56, 5775.
  (e) Khanbabaee, K. ; Basceken, S. ; Fl rke, U. Eur. J. Org. Chem. 2007, 831.
7. [7]
  (a) Imai, Y. ; Zhang, W. ; Kida, T. ; Nakatsuji, Y. ; Ikeda, I. Tetrahedron Lett. 1997, 38, 2681.
  (b) Imai, Y. ; Zhang, W. ; Kida, T. ; Nakatsuji, Y. ; Ikeda, I. J. Org. Chem. 2000, 65, 3326.
  (c) Gómez, M. ; Jansat, S. ; Muller, G. ; Maestro, M. A. ; Mahía, J. Organometallics 2002, 21, 1077.
  (d) Zhang, W. ; Xie, F. ; Matsuo, S. ; Imahori, Y. ; Kida, T. ; Nakatsuji, Y. ; Ikeda, I. Tetrahedron: Asymmetry 2006, 17, 767.
  (e) Zhang, Y. J. ; Wang, F. ; Zhang, W. J. Org. Chem. 2007, 72, 9208.
  (f) Wang, F. ; Zhang, Y. J. ; Wei, H. ; Zhang, J. ; Zhang, W. Tetrahedron Lett. 2007, 48, 4083.
  (g) Wang, F. ; Zhang, Y. J. ; Yang, G. ; Zhang, W. Tetrahedron Lett. 2007, 48, 4179.
  (h) Wang, F. ; Yang, G. ; Zhang, Y. J. ; Zhang, W. Tetrahedron 2008, 64, 9413.
  (i) Jiang, F. ; Wu, Z. ; Yang, G. ; Xie, F. ; Zhang, W. Tetrahedron Lett. 2011, 52, 2844.
  (j) Liu, Q. ; Wen, K. ; Zhang, Z. ; Wu, Z. ; Zhang, Y. J. ; Zhang, W. Tetrahedron 2012, 68, 5209.
  (k) Samadi, S. ; Jadidi, K. ; Notash, B. Tetrahedron: Asymmetry 2013, 24, 269.
8. [8]
  (a) Hsiao, Y. ; Hegedus, L. S. J. Org. Chem. 1997, 62, 3586.
  (b) Boland, N. A. ; Casey, M. ; Hynes, S. J. ; Matthews, J. W. ; Smyth, M. P. J. Org. Chem. 2002, 67, 3919.
  (c) Fujioka, H. ; Murai, K. ; Ohba, Y. ; Hiramatsu, A. ; Kita, Y. Tetrahedron Lett. 2005, 46, 2197.
  (d) Elders, N. ; Schmitz, B. F. ; de Kanter, F. J. J. ; Ruijter, E. ; Groen, M. B. ; Orru, R. V. A. J. Org. Chem. 2007, 72, 6135.
  (e) Liu, H. ; Du, D. -M. Adv. Synth. Catal. 2009, 351, 489.
9. [9]
  (a) Boland, N. A. ; Casey, M. ; Hynes, S. J. ; Matthews, J. W. ; Müller-Bunz, H. ; Wilkes, P. Org. Biomol. Chem. 2004, 2, 1995.
  (b) Nakamura, S. ; Hyodo, K. ; Nakamura, Y. ; Shibata, N. ; Toru, T. Adv. Synth. Catal. 2008, 350, 1443.
  (c) Takizawa, S. ; Hirata, S. ; Murai, K. ; Fujioka, H. ; Sasai, H. Org. Biomol. Chem. 2014, 12, 5827.
  (d) Hyodo, K. ; Nakamura, S. ; Shibata, N. Angew. Chem., Int. Ed. 2012, 51, 10337.
  (e) Arai, T. ; Moribatake, T. ; Masu, H. Chem. Eur. J. 2015, 21, 10671.
  (f) Kondo, M. ; Nishi, T. ; Hatanaka, T. ; Funahashi, Y. ; Nakamura, S. Angew. Chem., Int. Ed. 2015, 54, 8198.
  (g) Hellmuth, T. ; Frey, W. ; Peters, R. Angew. Chem., Int. Ed. 2015, 54, 2788.
10. [10]
  (a) Hao, X. -Q. ; Gong, J. -F. ; Du, C. -X. ; Wu, L. -Y. ; Wu, Y. -J. ; Song, M. -P. Tetrahedron Lett. 2006, 47, 5033.
  (b) Wu, L. -Y. ; Hao, X. -Q. ; Xu, Y. -X. ; Jia, M. -Q. ; Wang, Y. -N. ; Gong, J. -F. ; Song, M. -P. Organometallics 2009, 28, 3369.
  (c) Hao, X. -Q. ; Xu, Y. -X. ; Yang, M. -J. ; Wang, L. ; Niu, J. -L. ; Gong, J. -F. ; Song, M. -P. Organometallics 2012, 31, 835.
11. [11]
  Hao, X.-Q.; Zhao, Y.-W.; Yang, J.-J.; Niu, J.-L.; Gong, J.-F.; Song, M.-P. Organometallics 2014, 33, 1801. doi: 10.1021/om500144b
12. [12]
  Shao, D.-D.; Niu, J.-L.; Hao, X.-Q.; Gong, J.-F.; Song, M.-P. Dalton Trans. 2011, 40, 9012. doi: 10.1039/c1dt10329f
13. [13]
  (a) Wang, T. ; Hao, X. -Q. ; Huang, J. -J. ; Niu, J. -L. ; Gong, J. -F. ; Song, M. -P. J. Org. Chem. 2013, 78, 8712.
  (b) Wang, T. ; Niu, J. -L. ; Liu, S. -L. ; Huang, J. -J. ; Gong, J. -F. ; Song, M. -P. Adv. Synth. Catal. 2013, 355, 927.
14. [14]
  For reviews, please see: (a) Niu, J. -L. ; Hao, X. -Q. ; Gong, J. -F. ; Song, M. -P. Dalton Trans. 2011, 40, 5135.
  (b) Hao, X. -Q. ; Niu, J. -L. ; Zhao, X. -M. ; Gong, J. -F. ; Song, M. -P. Chin. J. Org. Chem. 2013, 33, 663(in Chinese).
15. [15]
  (a) Ullmann, F. ; Bielecki, J. Chem. Ber. 1901, 34, 2174.
  (b) Carlin, R. B. ; Swakon, E. A. J. Am. Chem. Soc. 1955, 77, 966.
16. [16]
  Hao, X.-Q.; Shen, M.-Z.; Jian, N.-G.; Pang, W.; Shen, X.-J.; Zhu, X.; Song, M.-P. Tetrahedron:Asymmetry 2016, 27, 163. doi: 10.1016/j.tetasy.2016.01.015
1. [1]
  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
2. [2]
  Zhaoyu Yan , Yuanhao Feng , Zhewen Ma , Wei Zheng . Chiroptical properties and supramolecular chirality transfer in a bilayer spironanographene. Chinese Chemical Letters, 2026, 37(10): 112890-. doi: 10.1016/j.cclet.2026.112890
3. [3]
  Yiming Yang , Lichao Sun , Qingfeng Zhang . Plasmonic nanocrystals with intrinsic chirality: Biomolecule-directed synthesis and applications. Chinese Journal of Structural Chemistry, 2025, 44(1): 100467-100467. doi: 10.1016/j.cjsc.2024.100467
4. [4]
  Fengying Ye , Ming Hu , Jun Luo , Wei Yu , Zhirong Xu , Jinjin Fu , Yansong Zheng . Significantly boosting circularly polarized luminescence by synergy of helical and planar chirality. Chinese Chemical Letters, 2025, 36(5): 110724-. doi: 10.1016/j.cclet.2024.110724
5. [5]
  Yue Pan , Jing Ren , Yifan Sun , Luying Lu , Jia Gao , Liping Chen , Shancheng Yan , Zhiyang Li . Harnessing chirality: A new dawn in inorganic nanomaterial synthesis and biomedical applications. Chinese Chemical Letters, 2026, 37(4): 110791-. doi: 10.1016/j.cclet.2024.110791
6. [6]
  Long Jin , Jian Han , Dongmei Fang , Min Wang , Jian Liao . Pd-catalyzed asymmetric carbonyl alkynylation: Synthesis of axial chiral ynones. Chinese Chemical Letters, 2024, 35(6): 109212-. doi: 10.1016/j.cclet.2023.109212
7. [7]
  Xiaoqian Wang , Yanling Shen , Long Chen , Lizhi Fang , Kuppusamy Kanagaraj , Ming Rao , Chunying Fan , Wanhua Wu , Cheng Yang . Azobenzene-winged phenanthroline for supramolecular chirality sensing and multidimensional chiroptical manipulation via solvent, light, temperature, and redox. Chinese Chemical Letters, 2026, 37(2): 111710-. doi: 10.1016/j.cclet.2025.111710
8. [8]
  Zhimin Sun , Shuo Guo , Jia-Qi Zhao , Ze-Qi Chen , Zhao-Xian Li , Chunju Li , He-Lue Sun . Switchable supramolecular chirality of phenylalanine-modified viologen within cucurbit[8]uril confinement. Chinese Chemical Letters, 2026, 37(7): 111823-. doi: 10.1016/j.cclet.2025.111823
9. [9]
  Yi-Kao Xu , Guo-Ping Luo , Liang-Bin Hu , Wei-Min He . Asymmetric Büchner reaction and arene cyclopropanation via copper-catalyzed controllable cyclization of diynes. Chinese Chemical Letters, 2025, 36(8): 111226-. doi: 10.1016/j.cclet.2025.111226
10. [10]
  Qianyun Ye , Yuanyuan Liang , Yuhe Yuan , Xiaohuan Sun , Liqi Zhu , Xuan Wu , Jie Han , Rong Guo . pH-responsive chiral supramolecular cysteine-Zn²⁺-indocyanine green assemblies for triple-level chirality-specific anti-tumor efficacy. Chinese Chemical Letters, 2025, 36(5): 110432-. doi: 10.1016/j.cclet.2024.110432
11. [11]
  Zhen-Qi Wang , Lin-Wen Wei , Zhao-Qing Wang , Yan-Jie Yang , Yu Zhao , Song Liu , Yuan Huang . Modular synthesis of polyfunctionalized axial-chiral 2-arylpyridines via cobalt-catalyzed asymmetric [2 + 2 + 2] cycloaddition of diynes and nitriles. Chinese Chemical Letters, 2026, 37(4): 111377-. doi: 10.1016/j.cclet.2025.111377
12. [12]
  Min Liu , Di Wang , Zenghui Ye , Donghao Jiang , Bencan Tang , Yanqi Wu , Fengzhi Zhang . Highly stereo- and enantio-selective synthesis of spiro cyclopropyl oxindoles via organic catalyst-mediated cyclopropanation. Chinese Chemical Letters, 2025, 36(10): 110923-. doi: 10.1016/j.cclet.2025.110923
13. [13]
  Xue-Lu Ma , Jun-Bo Lu , Yuan Zhang , Ya-Fei Jiang , Jun Li . Dinitrogen fixation on transition metal complexes with flexible axial bonding. Chinese Journal of Structural Chemistry, 2026, 45(3): 100831-100831. doi: 10.1016/j.cjsc.2025.100831
14. [14]
  Yu-Long Peng , Zhi-Yong Qiu , Peng Liu , Zhe Dong , Jun-Yong Wu , Fang Yang , Zai-Fang Li , Shi-Yong Liu . Tuning fluorination patterns on the central benzene core of acceptors for high-efficiency ternary organic solar cells. Chinese Journal of Structural Chemistry, 2026, 45(5): 100886-100886. doi: 10.1016/j.cjsc.2026.100886
15. [15]
  Yutong Chen , Shuting Guo , Mingrui Fan , Songlin Yang , Qiuxia Lin , Jiafeng Zou , Junyuan Xu , Tongtong Zheng , Kangtai He , Feng Gao , Yanzuo Chen . Exosome-liposome hybrid system with antioxidant and anti-inflammatory activities targeting glial cells for the treatment of central nervous system diseases. Chinese Chemical Letters, 2026, 37(9): 112027-. doi: 10.1016/j.cclet.2025.112027
16. [16]
  Chunhui Wang , Zhe Han , Yuan Gao , Chaoyue Fan , Puyong He , Bojun Li , Dong Ma , Yang Zhang , Lei Zhang , Jie Qiu . Aluminate-mediated assembly of Keggin-type thorium-oxo clusters with a substitutable central octahedron and tunable shell ligands. Chinese Chemical Letters, 2026, 37(10): 111563-. doi: 10.1016/j.cclet.2025.111563
17. [17]
  Yanan Zhou , Li Sheng , Lanlan Chen , Wenhua Zhang , Jinlong Yang . Axial coordinated iron-nitrogen-carbon as efficient electrocatalysts for hydrogen evolution and oxygen redox reactions. Chinese Chemical Letters, 2025, 36(1): 109588-. doi: 10.1016/j.cclet.2024.109588
18. [18]
  Ze Zhang , Lei Yang , Jin-Ru Liu , Hao Hu , Jian-Li Mi , Chao Su , Bei-Bei Xiao , Zhi-Min Ao . Improved oxygen electrocatalysis at FeN₄ and CoN₄ sites via construction of axial coordination. Chinese Chemical Letters, 2025, 36(2): 110013-. doi: 10.1016/j.cclet.2024.110013
19. [19]
  Wenjie Zhang , Jiong Zhou . Enhanced oxygen reduction through axial chlorine engineering of p-block antimony atomic sites. Chinese Journal of Structural Chemistry, 2026, 45(1): 100732-100732. doi: 10.1016/j.cjsc.2025.100732
20. [20]
  Hongjin Xu , Jinghua Wu , Hui Wang , Huanfeng Jiang , Zhiqiang Ma . Asymmetric total synthesis of (–)-14-epi-sinugyrosanolide A. Chinese Chemical Letters, 2026, 37(3): 112018-. doi: 10.1016/j.cclet.2025.112018

Get Citation

PDF

XML

Metrics

PDF Downloads(13)
Abstract views(3384)
HTML views(263)

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