Citation: Zhao Sen, Li Chunpu, Xu Bin, Liu Hong. Cp*Rh(Ⅲ)-Catalyzed C—H 3, 3-Difluoroallylation of Indoles and N-Iodosuccinimide-Mediated Cyclization for the Synthesis of Fluorinated 3, 4-Dihydropyrimido-[1, 6-a]-indol-1(2H)-one Derivatives[J]. Chinese Journal of Organic Chemistry, ;2020, 40(6): 1549-1562. doi: 10.6023/cjoc202004039 shu

Cp*Rh(Ⅲ)-Catalyzed C—H 3, 3-Difluoroallylation of Indoles and N-Iodosuccinimide-Mediated Cyclization for the Synthesis of Fluorinated 3, 4-Dihydropyrimido-[1, 6-a]-indol-1(2H)-one Derivatives

Zhao Sen ^a,b,c ,
Li Chunpu ^b,c ,
Xu Bin ^a,, ,
Liu Hong ^b,c,,

a.
Department of Chemistry, College of Sciences, Shanghai University, Shanghai 200444
b.
State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai 201203
c.
Key Laboratory of Receptor Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai 201203

Corresponding author: Xu Bin, xubin@shu.edu.cn Liu Hong, hliu@simm.ac.cn
Received Date: 25 April 2020
Revised Date: 30 April 2020
Available Online: 5 May 2020
Fund Project: the Strategic Priority Research Program of the Chinese Academy of Sciences XDA12050411the National Natural Science Foundation of China 81220108025the National Natural Science Foundation of China 91229204the National Natural Science Foundation of China 81620108027the Strategic Priority Research Program of the Chinese Academy of Sciences XDA12020375the National Natural Science Foundation of China 21632008Project supported by the National Natural Science Foundation of China (Nos. 81620108027, 21632008, 91229204, 81220108025) and the Strategic Priority Research Program of the Chinese Academy of Sciences (Nos. XDA12020375, XDA12050411)

Figures(6)

A mild and facile two-step strategy has been developed for the synthesis of fluorinated 3, 4-dihydropyrimido-[1, 6-a]-indol-1(2H)-ones through Cp*Rh(Ⅲ)-catalyzed C-H 3, 3-difluoroallylation and N-iodosuccinimide (NIS)-mediated cyclization. This strategy featured broad synthetic generality, unique versatility and high efficiency, which provided a potential tool for the construction of fluorine-containing heterocycles for drug discovery.
- C-H activation,
- fluorine chemistry,
- rhodium catalysis
1. [1]
  (a) Mizuta, M.; Seio, K.; Miyata, K.; Sekine, M. J. Org. Chem. 2007, 72, 5046.
  (b) Bandurco, V. T.; Wong, E. M.; Levine, S. D.; Hajos, Z. G. J. Med. Chem. 1981, 24, 1455.
  (c) Hammer, H.; Winterfeldt, E. Tetrahedron 1981, 37, 3609.
  (d) Kato, M.; Nishino, S.; Iro, K.; Yamakuni, H.; Takasugi, H. Chem. Pharm. Bull. 1994, 42, 2556.
  (e) Wright, W. B.; Brabander, H. J. J. Med. Chem. 1968, 11, 1164.
2. [2]
  (a) Zhang, Y.; Zheng, J.; Cui, S. J. Org. Chem. 2014, 79, 6490.
  (b) Zheng, J.; Zhang, Y.; Cui, S. Org. Lett. 2014, 16, 3560.
  (c) Chen, X.; Hu, X.; Bai, S.; Deng, Y.; Jiang, H.; Zeng, W. Org. Lett. 2016, 18, 192.
3. [3]
  (a) Muller, K.; Faeh, C.; Diederich, F. Science 2007, 317, 1881.
  (b) Hagmann, W. K. J. Med. Chem. 2008, 51, 4359.
  (c) Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, V. Chem. Soc. Rev. 2008, 37, 320.
  (d) Wang, J.; Sánchez-Roselló, M.; Aceña, J. L.; del Pozo, C.; Sorochinsky, A. E.; Fustero, S.; Soloshonok, V. A.; Liu, H. Chem. Rev. 2014, 114, 2432.
  (e) Zhou, Y.; Wang, J.; Gu, Z.; Wang, S.; Zhu, W.; Aceña, J. L.; Soloshonok, V. A.; Izawa, K.; Liu, H. Chem. Rev. 2016, 116, 422.
4. [4]
  (a) Price, D. A.; Armour, D.; de Groot, M.; Leishman, D.; Napier, C.; Perros, M.; Stammen, B. L.; Wood, A. Bioorg. Med. Chem. Lett. 2006, 16, 4633.
  (b) Xue, F.; Li, H.; Delker, S. L.; Fang, J.; Martásek, P.; Roman, L. J.; Poulos, T. L.; Silverman, R. B. J. Am. Chem. Soc. 2010, 132, 14229.
  (c) Zhou, Q.; Ruffoni, A.; Gianatassio, R.; Fujiwara, Y.; Sella, E.; Shabat, D.; Baran, P. S. Angew. Chem., Int. Ed. 2013, 52, 3949.
  (d) Massa, M. A.; Spangler, D. P.; Durley, R. C.; Hickory, B. S.; Connolly, D. T.; Witherbee, B. J.; Smith, M. E.; Sikorski, J. A. Bioorg. Med. Chem. Lett. 2001, 11, 1625.
5. [5]
  Middleton, W. J.; Bingham, E. M. J. Org. Chem. 1980, 45, 2883. doi: 10.1021/jo01302a025
6. [6]
  (a) Fujita, T.; Sugiyama, K.; Sanada, S.; Ichitsuka, T.; Ichikawa, J. Org. Lett. 2016, 18, 248.
  (b) S. Akiyama, S.; Kubota, K.; Mikus, M. S.; Paioti, P. H. S.; Romiti, F.; Liu, Q.; Zhou, Y.; Hoveyda, A. H.; Ito, H. Angew. Chem., Int. Ed. 2019, 58, 11998.
  (c) Cogswell, T. J.; Dahlen A.; Knerr, L. Chem.-Eur. J. 2019, 25, 1184.
7. [7]
  Min, Q. Q.; Yin, Z.; Feng, Z.; Guo, W. H.; Zhang, X. J. Am. Chem. Soc. 2014, 136, 1230. doi: 10.1021/ja4114825
8. [8]
  Li, C.; Zhang, D.; Zhu, W.; Wan, P.; Liu, H. Org. Chem. Front. 2016, 3, 1080. doi: 10.1039/C6QO00178E
9. [9]
  Ni, J.; Zhao, H.; Zhang, A. Org. Lett. 2017, 19, 3159. doi: 10.1021/acs.orglett.7b01282
10. [10]
  (a) Wu, X.; Wang, B.; Zhou, S.; Zhou, Y.; Liu, H. ACS Catal. 2017, 7, 2494.
  (b) Wu, X.; Wang, B.; Zhou, Y.; Liu, H. Org. Lett. 2017, 19, 1294.
  (c) Xie, Y.; Wu, X.; Li, C.; Wang, J.; Li, J.; Liu, H. J. Org. Chem. 2017, 82, 5263.
  (d) Fei, X.; Li, C.; Yu X.; Liu, H. J. Org. Chem. 2019, 84, 6840.
  (e) Yang, L.; Li, C.; Wang, D.; Liu, H. J. Org. Chem. 2019, 84, 7320.
11. [11]
  (a) Dai, H.; Yu, C.; Wang, Z.; Yan, H.; Lu, C. Org. Lett. 2016, 18, 3410.
  (b) Dutta, U.; Deb, A.; Lupton, D. W.; Maiti, D. Chem. Commun. 2015, 51, 17744.
12. [12]
  (a) Zhang, L.; Zhu, M.; Ni, S.; Wen, L.; Li, M. ACS Catal. 2019, 9, 1680.
  (b) Kong, W.; Chen, X.; Wang, M.; Dai, H.; Yu, J. Org. Lett. 2018, 20, 284.
13. [13]
  Nihei, T.; Iwai, N.; Matsuda, T.; Kitazume, T. J. Org. Chem. 2005, 70, 5912. doi: 10.1021/jo050634u
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