Citation: Yu Wenquan, Song Lina, Tian Xianhai, Zhao Ting, Wang Manman, Wu Jie, Qiao Yan, Chang Junbiao. Synthesis of 3-Acyl and 2-Acyl Imidazo [1, 2-a]pyridines by I₂-Mediated Diamination of α, β-Unsaturated Ketones with 2-Aminopyridines[J]. Chinese Journal of Organic Chemistry, ;2018, 38(6): 1530-1537. doi: 10.6023/cjoc201712045 shu

Synthesis of 3-Acyl and 2-Acyl Imidazo [1, 2-a]pyridines by I₂-Mediated Diamination of α, β-Unsaturated Ketones with 2-Aminopyridines

Yu Wenquan ^a,, ,
Song Lina ^a ,
Tian Xianhai ^a ,
Zhao Ting ^a ,
Wang Manman ^a ,
Wu Jie ^a ,
Qiao Yan ^b ,
Chang Junbiao ^a,,

a.
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001
b.
School of Basic Medical Sciences, Zhengzhou University, Zhengzhou 450001

Corresponding author: Yu Wenquan, wenquan_yu@zzu.edu.cn Chang Junbiao, changjunbiao@zzu.edu.cn
Received Date: 31 December 2017
Revised Date: 11 January 2018
Available Online: 6 June 2018
Fund Project: Project supported by the National Natural Science Foundation of China (No. 81330075) and the Outstanding Young Talent Research Fund of Zhengzhou University (No. 1521316004)the National Natural Science Foundation of China 81330075the Outstanding Young Talent Research Fund of Zhengzhou University 1521316004

Figures(1)

Employing molecular iodine as the sole oxidant, a new and transition metal-free diamination reaction of α, β-unsaturated ketones with 2-aminopyridines has been developed. It can not only produce 3-acyl imidazo[1, 2-a]pyridines but can also generate novel 2-acyl derivatives regioselectively by changing the solvent and substituents in the 2-aminopyridine substrates.
- molecular iodine,
- transition metal-free,
- diamination,
- imidazo[1, 2-a]pyridine,
- regioselective
1. [1]
  (a) Zhu, Y. -P. ; Fei, Z. ; Liu, M. -C. ; Jia, F. -C. ; Wu, A. -X. Org. Lett. 2013, 15, 378.
  (b) Zhu, Y. -P. ; Liu, M. -C. ; Cai, Q. ; Jia, F. -C. ; Wu, A. -X. Chem. -Eur. J. 2013, 19, 10132.
  (c) Gao, Q. ; Liu, S. ; Wu, X. ; Zhang, J. ; Wu, A. Org. Lett. 2015, 17, 2960.
2. [2]
  (a) Huo, C. ; Tang, J. ; Xie, H. ; Wang, Y. ; Dong, J. Org. Lett. 2016, 18, 1016.
  (b) Roslan, I. I. ; Ng, K. -H. ; Chuah, G. -K. ; Jaenicke, S. Adv. Synth. Catal. 2016, 358, 364.
  (c) Ma, L. ; Wang, X. ; Yu, W. ; Han, B. Chem. Commun. 2011, 47, 11333.
  (d) Wang, X. ; Ma, L. ; Yu, W. Synthesis 2011, 2445.
  (e) Cao, H. ; Liu, X. ; Liao, J. ; Huang, J. ; Qiu, H. ; Chen, Q. ; Chen, Y. J. Org. Chem. 2014, 79, 11209.
  (f) Zhan, H. ; Zhao, L. ; Liao, J. ; Li, N. ; Chen, Q. ; Qiu, S. ; Cao, H. Adv. Synth. Catal. 2015, 357, 46
3. [3]
  (a) Monir, K. ; Bagdi, A. K. ; Mishra, S. ; Majee, A. ; Hajra, A. Adv. Synth. Catal. 2014, 356, 1105.
  (b) Mishra, S. ; Monir, K. ; Mitra, S. ; Hajra, A. Org. Lett. 2014, 16, 6084.
4. [4]
  Zhu, Y.; Li, C.; Zhang, J.; She, M.; Sun, W.; Wan, K.; Wang, Q.; Yin, B.; Liu, P.; Li, J. Org. Lett. 2015, 17, 3872. doi: 10.1021/acs.orglett.5b01854
5. [5]
  (a) Nguyen, T. B. ; Corbin, M. ; Retailleau, P. ; Ermolenko, L. ; Al-Mourabit, A. Org. Lett. 2015, 17, 4956.
  (b) Nguyen, T. B. ; Ermolenko, L. ; Retailleau, P. ; Al-Mourabit, A. Org. Lett. 2016, 18, 2177.
6. [6]
  (a) Couty, F. ; Evano, G. In Comprehensive Heterocyclic Chemistry Ⅲ, Vol. 11, Eds. : Katritzky, A. R. ; Ramsden, C. A. ; Scriven, E. F. V. ; Taylor, R. J. K., Elsevier, Oxford, 2008, pp. 409~499.
  (b) Bagdi, A. K. ; Santra, S. ; Monir, K. ; Hajra, A. Chem. Commun. 2015, 51, 1555.
  (c) Dymińska, L. Bioorg. Med. Chem. 2015, 23, 6087.
  (d) Enguehard-Gueiffier, C. ; Gueiffier, A. Mini-Rev. Med. Chem. 2007, 7, 888.
7. [7]
  (a) Mizushige, K. ; Ueda, T. ; Yukiiri, K. ; Suzuki, H. Cardiovasc. Drug Rev. 2002, 20, 163.
  (b) Igawa, H. ; Takahashi, M. ; Kakegawa, K. ; Kina, A. ; Ikoma, M. ; Aida, J. ; Yasuma, T. ; Kawata, Y. ; Ashina, S. ; Yamamoto, S. ; Kundu, M. ; Khamrai, U. ; Hirabayashi, H. ; Nakayama, M. ; Nagisa, Y. ; Kasai, S. ; Maekawa, T. J. Med. Chem. 2016, 59, 1116.
  (c) Trabanco, A. A. ; Tresadern, G. ; Macdonald, G. J. ; Vega, J. A. ; Lucas, A. I. ; Matesanz, E. ; García, A. ; Linares, M. L. ; Diego, S. A. A. ; Alonso, J. M. ; Oehlrich, D. ; Ahnaou, A. ; Drinkenburg, W. ; Mackie, C. ; Andrés, J. I. ; Lavreysen, H. ; Cid, J. J. Med. Chem. 2012, 55, 2688.
  (d) Gladysz, R. ; Adriaenssens, Y. ; Winter, H. D. ; Joossens, J. ; Lambeir, A. ; Augustyns, K. ; Veken, P. V. J. Med. Chem. 2015, 58, 9238.
8. [8]
  (a) Song, G. ; Zhang, Y. ; Li, X. Organometallics 2008, 27, 1936.
  (b) John, A. ; Shaikh, M. M. ; Ghosh, P. Dalton Trans. 2009, 10581.
  (c) Ke, C. -H. ; Kuo, B. -C. ; Nandi, D. ; Lee, H. M. Organometallics 2013, 32, 4775.
9. [9]
  (a) Stasyuk, A. J. ; Banasiewicz, M. ; Cyrański, M. K. ; Gryko, D. T. J. Org. Chem. 2012, 77, 5552.
  (b) Mutai, T. ; Sawatani, H. ; Shida, T. ; Shono, H. ; Araki, K. J. Org. Chem. 2013, 78, 2482.
  (c) Firmansyah, D. ; Ciuciu, A. I. ; Hugues, V. ; Blanchard-Desce, M. ; Flamigni, L. ; Gryko, D. T. Chem. -Asian J. 2013, 8, 1279.
  (d) Furukawa, S. ; Shono, H. ; Mutai, T. ; Araki, K. ACS Appl. Mater. Interfaces 2014, 6, 16065.
  (e) Nagarajan, N. ; Velmurugan, G. ; Prakash, A. ; Shakti, N. ; Katiyar, M. ; Venuvanalingam, P. ; Renganathan, R. Chem. -Asian J. 2014, 9, 294.
  (f) Yao, C. ; Xue, Z. ; Lian, M. ; Xu, X. ; Zhao, J. ; Zhou, G. ; Wu, Y. ; Yu, D. ; Wong, W. -Y. J. Organomet. Chem. 2015, 784, 31.
10. [10]
  (a) Kang, S. ; Kim, R. Y. ; Seo, M. J. ; Lee, S. ; Kim, Y. M. ; Seo, M. ; Seo, J. J. ; Ko, Y. ; Choi, I. ; Jang, J. ; Nam, J. ; Park, S. ; Kang, H. ; Kim, H. J. ; Kim, J. ; Ahn, S. ; Pethe, K. ; Nam, K. ; No, Z. ; Kim, J. J. Med. Chem. 2014, 57, 52935.
  (b) Hirayama, T. ; Okaniwa, M. ; Banno, H. ; Kakei, H. ; Ohashi, A. ; Iwai, K. ; Ohori, M. ; Mori, K. ; Gotou, M. ; Kawamoto, T. ; Yokota, A. ; Ishikawa, T. J. Med. Chem. 2015, 58, 8036.
  (c) Moraski, G. C. ; Miller, P. A. ; Bailey, M. A. ; Ollinger, J. ; Parish, T. ; Boshoff, H. I. ; Cho, S. ; Anderson, J. R. ; Mulugeta, S. ; Franzblau, S. G. ; Miller, M. J. ACS Infect. Dis. 2015, 1, 85.
  (d) Li, R. ; Wang, H. ; Li, Y. ; Wang, Z. ; Wang, X. ; Wang, Y. ; Ge, Z. ; Li, R. Eur. J. Med. Chem. 2015, 93, 381.
  (e) Jaramillo, C. ; de Diego, J. E. ; Hamdouchi, C. ; Collins, E. ; Keyser, H. ; Sánchez-Martínez, C. ; del Prado, M. ; Norman, B. ; Brooks, H. B. ; Watkins, S. A. ; Spencer, C. D. ; Dempsey, J. A. ; Anderson, B. D. ; Campbell, R. M. ; Leggett, T. ; Patel, B. ; Schultz, R. M. ; Espinosa, J. ; Vieth, M. ; Zhang, F. ; Timm, D. E. Bioorg. Med. Chem. Lett. 2004, 14, 6095.
  (f) Sanfilippo, P. J. ; Urbanski, M. ; Press, J. B. ; Dubinsky, B. ; Moore, J. B. J. Med. Chem. 1988, 31, 2221.
11. [11]
  (a) Starrett, J. E. Montzka, T. A. ; Crosswell, A. R. ; Cavanagh, R. L. J. Med. Chem. 1989, 32, 2204.
  (b) Anderson, M. ; Beattie, J. F. ; Breault, G. A. ; Breed, J. ; Byth, K. F. ; Culshaw, J. D. ; Ellston, R. P. A. ; Green, S. ; Minshull, C. A. ; Norman, R. A. ; Pauptit, R. A. ; Stanway, J. ; Thomas, A. P. ; Jewsbury, P. J. Bioorg. Med. Chem. Lett. 2003, 13, 3021.
12. [12]
  Podergajs, S.; Stanovnik, B.; Tišler, M. Synthesis 1984, 263.
13. [13]
  For representative examples, see:(a) Wang, H.; Wang, Y.; Liang, D.; Liu, L.; Zhang, J.; Zhu, Q. Angew. Chem., Int. Ed. 2011, 50, 5678.
  (b) Mohan, D. C.; Rao, S. N.; Adimurthy, S. J. Org. Chem. 2013, 78, 1266.
  (c) Reddy, K. R.; Reddy, A. S.; Shankar, R.; Kant, R.; Das, P. Asian J. Org. Chem. 2015, 4, 573.
  (d) Kaswan, P.; Pericherla, K.; Saini, H. K.; Kumar, A. RSC Adv. 2015, 5, 3670.
  (e) Kaswan, P.; Pericherla, K.; Rajnikant; Kumar, A. Tetrahedron 2014, 70, 8539.
  (f) Xing, M.-M.; Xin, M.; Shen, C.; Gao, J.-R.; Jia, J.-H.; Li, Y.-J. Tetrahedron 2016, 72, 4201.
  (g) Meng, X.; Zhang, J.; Chen, B.; Jing, Z.; Zhao, P. Catal. Sci. Technol. 2016, 6, 890.
  (h) Yan, R.-L.; Yan, H.; Ma, C.; Ren, Z.-Y.; Gao, X.-A.; Huang, G.-S.; Liang, Y.-M. J. Org. Chem. 2012, 77, 2024.
14. [14]
  (a) Tian, X. ; Song, L. Wang, Manman. ; Lv, Z. ; Wu, J. ; Yu, W. ; Chang, J. Chem. -Eur. J. 2016, 22, 7617.
  (b) Liu, J. ; Wei, W. ; Zhao, T. ; Liu, X. ; Wu, J. ; Yu, W. ; Chang, J. J. Org. Chem. 2016, 81, 9326.
15. [15]
  Li, J. ; Zhu, Y. ; Li, C. ; Liu, P. ; Wang, Y. CN 105801575, 2016[Chem. Abstr. 2016, 165, 274501. ]
16. [16]
  CCDC 1539194(3a) and 1539195(4s) contain the supplementary crystallographic data for this paper. These data are provided free of charge by The Cambridge Crystallographic Data Centre.
17. [17]
  (a) King, L. C. J. Am. Chem. Soc. 1944, 66, 894.
  (b) Pearson, R. G. J. Am. Chem. Soc. 1947, 69, 3100.
1. [1]
  Chunhua Ma , Mengjiao Liu , Siyu Ouyang , Zhenwei Cui , Jingjing Bi , Yuqin Jiang , Zhiguo Zhang . Metal-free construction of diverse 1,2,4-triazolo[1,5-a]pyridines on water. Chinese Chemical Letters, 2025, 36(1): 109755-. doi: 10.1016/j.cclet.2024.109755
2. [2]
  Bofei JIA , Zhihao LIU , Zongyuan GAO , Shuai ZHOU , Mengxiang WU , Qian ZHANG , Xiamei ZHANG , Shuzhong CHEN , Xiaohan YANG , Yahong LI . Cu(Ⅱ) and Cu(Ⅰ) complexes based on derivatives of imidazo[1,5-a]pyridine: Synthesis, structures, in situ metal-ligand reactions, and catalytic activity. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 1020-1036. doi: 10.11862/CJIC.20240317
3. [3]
  Wujun Jian , Mong-Feng Chiou , Yajun Li , Hongli Bao , Song Yang . Cu-catalyzed regioselective diborylation of 1,3-enynes for the efficient synthesis of 1,4-diborylated allenes. Chinese Chemical Letters, 2024, 35(5): 108980-. doi: 10.1016/j.cclet.2023.108980
4. [4]
  Yaqi Deng , Jian Xue , Xiang Wu , Shunying Liu . Highly regioselective electrochemical oxidative 2,1-azolization of alkenes with azoles and nucleophiles. Chinese Chemical Letters, 2025, 36(9): 110822-. doi: 10.1016/j.cclet.2025.110822
5. [5]
  Xiaodan Wang , Yingnan Liu , Zhibin Liu , Zhongjian Li , Tao Zhang , Yi Cheng , Lecheng Lei , Bin Yang , Yang Hou . Highly efficient electrosynthesis of H₂O₂ in acidic electrolyte on metal-free heteroatoms co-doped carbon nanosheets and simultaneously promoting Fenton process. Chinese Chemical Letters, 2024, 35(7): 108926-. doi: 10.1016/j.cclet.2023.108926
6. [6]
  Yong-Xing Tang , Yi-Ran Wu , Li-Sheng Wang , Chun-Yan Wu , Yu-Man Song , You Zhou , An-Xin Wu . I₂-DMSO mediated bicyclization of o-alkynylanilines: Chemo- and regioselective construction of fused tetracyclic N-heterocycles. Chinese Chemical Letters, 2026, 37(11): 112367-. doi: 10.1016/j.cclet.2026.112367
7. [7]
  Tao Zhou , Jing Zhou , Yunyun Liu , Jie-Ping Wan , Fen-Er Chen . Transition metal-free tunable synthesis of 3-(trifluoromethylthio) and 3-trifluoromethylsulfinyl chromones via domino C–H functionalization and chromone annulation of enaminones. Chinese Chemical Letters, 2024, 35(11): 109683-. doi: 10.1016/j.cclet.2024.109683
8. [8]
  Jiao Chen , Zihan Zhang , Guojin Sun , Yudi Cheng , Aihua Wu , Zefan Wang , Wenwen Jiang , Fulin Chen , Xiuying Xie , Jianli Li . Benzo[4,5]imidazo[1,2-a]pyrimidine-based structure-inherent targeting fluorescent sensor for imaging lysosomal viscosity and diagnosis of lysosomal storage disorders. Chinese Chemical Letters, 2024, 35(11): 110050-. doi: 10.1016/j.cclet.2024.110050
9. [9]
  Yanxin Jiang , Kwai Wun Cheng , Zhiping Yang , Jun (Joelle) Wang . Pd-catalyzed enantioselective and regioselective asymmetric hydrophosphorylation and hydrophosphinylation of enynes. Chinese Chemical Letters, 2025, 36(5): 110231-. doi: 10.1016/j.cclet.2024.110231
10. [10]
  Junhua Li , Tianci Shen , Yahui Zhuang , Yu Fu , Yian Shi . Pd-Catalyzed highly regioselective migratory hydroesterification of internal olefins with formates. Chinese Chemical Letters, 2025, 36(7): 110599-. doi: 10.1016/j.cclet.2024.110599
11. [11]
  Ping Zhang , Hongyuan Ren , Zhaofeng Sun , Hou-Ji Cao , Deshuang Tu , Chang-Sheng Lu , Jordi Poater , Miquel Solà , Hong Yan . Facile and regioselective B–H bond functionalization of carboranes via cage···Ⅰ(Ⅲ) interaction. Chinese Chemical Letters, 2026, 37(5): 111617-. doi: 10.1016/j.cclet.2025.111617
12. [12]
  Chunxiu Yu , Zelin Wu , Hongle Shi , Lingyun Gu , Kexin Chen , Chuan-Shu He , Yang Liu , Heng Zhang , Peng Zhou , Zhaokun Xiong , Bo Lai . Insights into the electron transfer mechanisms of peroxydisulfate activation by modified metal-free acetylene black for degradation of sulfisoxazole. Chinese Chemical Letters, 2024, 35(8): 109334-. doi: 10.1016/j.cclet.2023.109334
13. [13]
  Lang Gao , Cen Zhou , Rui Wang , Feng Lan , Bohang An , Xiaozhou Huang , Xiao Zhang . Unveiling inverse vulcanized polymers as metal-free, visible-light-driven photocatalysts for cross-coupling reactions. Chinese Chemical Letters, 2024, 35(4): 108832-. doi: 10.1016/j.cclet.2023.108832
14. [14]
  Xiuwen Xu , Quan Zhou , Yacong Wang , Yunjie He , Qiang Wang , Yuan Wang , Bing Chen . Expanding the toolbox of metal-free organic halide perovskite for X-ray detection. Chinese Chemical Letters, 2024, 35(9): 109272-. doi: 10.1016/j.cclet.2023.109272
15. [15]
  Kexin Yin , Jingren Yang , Yanwei Li , Qian Li , Xing Xu . Metal-free diatomaceous carbon-based catalyst for ultrafast and anti-interference Fenton-like oxidation. Chinese Chemical Letters, 2024, 35(12): 109847-. doi: 10.1016/j.cclet.2024.109847
16. [16]
  Lingdan Kong , Pingping Huang , Feng Yuan , Yue Zhang , Xiaoqian Shi , Kang Han , Keke Liu , Qing Xu , Wenjing Zhang , Tom Lawson , Xiaoru Xia , Yong Liu , Yuepeng Jin . A metal-free bionic nanozyme for efficient inhibition of cancer recurrence and metastasis following photothermal therapy. Chinese Chemical Letters, 2025, 36(9): 111030-. doi: 10.1016/j.cclet.2025.111030
17. [17]
  Congxu Wang , Xuan Xie , Feng Qiu , Lei Zhu , Imran Shakir , Yuxi Xu . Recent advances in photocatalytic overall production of hydrogen peroxide from metal-free photocatalysts. Chinese Chemical Letters, 2026, 37(1): 111604-. doi: 10.1016/j.cclet.2025.111604
18. [18]
  Tong Yue , Jun-Bo Wang , Xin-Yue Wang , Ming-Yi Huang , Mo Zhang , Zhan-Hui Zhang . Metal-free carbon quantum dots as photocatalyst for phosphonation of undirected heteroaryl compounds. Chinese Chemical Letters, 2026, 37(8): 112050-. doi: 10.1016/j.cclet.2025.112050
19. [19]
  Muhammad Riaz , Rakesh Kumar Gupta , Di Sun , Mohammad Azam , Ping Cui . Selective adsorption of organic dyes and iodine by a two-dimensional cobalt(II) metal-organic framework. Chinese Journal of Structural Chemistry, 2024, 43(12): 100427-100427. doi: 10.1016/j.cjsc.2024.100427
20. [20]
  Ming-Chang Wang , Zhi Lin , Jia-Jia Li , Jia-Min Lian , Yun-Xia Hu , Yan Chen , Ke-Zhao Du , Jin Chen . Bromine for iodine: Unlocking short-wavelength UV phase matching in nonlinear optical metal halides. Chinese Chemical Letters, 2026, 37(10): 111639-. doi: 10.1016/j.cclet.2025.111639

Get Citation

PDF

XML

Metrics

PDF Downloads(19)
Abstract views(2018)
HTML views(253)

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

Synthesis of 3-Acyl and 2-Acyl Imidazo [1, 2-a]pyridines by I2-Mediated Diamination of α, β-Unsaturated Ketones with 2-Aminopyridines

Metrics

通讯作者: 陈斌, bchen63@163.com

Synthesis of 3-Acyl and 2-Acyl Imidazo [1, 2-a]pyridines by I₂-Mediated Diamination of α, β-Unsaturated Ketones with 2-Aminopyridines