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Chinese Journal of Organic Chemistry >

2021 , Vol. 41 >Issue 7: 2684 - 2692

DOI: https://doi.org/10.6023/cjoc202103004

ARTICLES

Photosensitizer-Free Visible-Light-Promoted Trifluoromethylation of Imidazo[1,2-a]pyridines

  • Ruichao Yao ,
  • Wenbo Chen ,
  • Qilong Shen
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  • a Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power, Shanghai University of Electric Power, Shanghai 200090
    b CAS Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
    c University of Chinese Academy of Sciences, Beijing 100049
* Corresponding authors. E-mail: ;

Received date: 2021-03-02

  Revised date: 2021-03-25

  Online published: 2021-04-12

Supported by

National Natural Science Foundation of China(21625206); Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000); Natural Science Foundation of Shanghai(20ZR1471600); Science and Technology Commission of Shanghai Municipality(19DZ2271100)

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Abstract

A photosensitizer-free visible-light-promoted method for direct trifluoromethylation of imidazo[1,2-a]pyridine derivatives using an electrophilic trifluoromethylating reagent based on sulfonium ylide skeleton was described. The reaction occurred in broad substrate scope under mild conditions and tolerant various functional groups. Initial mechanistic experiments including reactions in the presence of radical scavengers and UV absorption spectroscopic studies were conducted. Inhibition by the radical scavengers were observed. In addition, an extra-absorption peak between 500~510 nm in UV-Vis absorption spectrum was observed. These observations led us to propose a working mechanism. Finally, application of the current method for the preparation of trifluoromethylated derivative of gastroproctive drug zolimidine was demonstrated.

Key words： trifluoromethyl; visible light; photosensitizer free; imidazo[1,2-a]pyridine

Cite this article

Ruichao Yao , Wenbo Chen , Qilong Shen . Photosensitizer-Free Visible-Light-Promoted Trifluoromethylation of Imidazo[1,2-a]pyridines[J]. Chinese Journal of Organic Chemistry, 2021 , 41(7) : 2684 -2692 . DOI: 10.6023/cjoc202103004

References

[1]
(a) Krause, M.; Foks, H.; Gobis, K. Molecules 2017, 22, 399, doi: 10.3390/molecules22030399.
[1]
(b) Bagdi,A. K.; Santra, S.; Monir, K.; Hajra, A. Chem. Commun. 2015, 51,1555.
[2]
Zivkovic, B.; Morel, E.; Joly, D.; Perrault, G.; Sanger,D. J.; Lloyd,K. G. Pharmacopsychiatry 1990, 23,108.
[3]
Bomalaski,M. N.; Claflin,E. S.; Townsend, W.; Peterson,M. D. JAMA Neurol. 2017, 74,1130.
[4]
Materia, A.; Basso, N.; Bagarani, M.; Basoli, A.; Speranza, V. Clin. Ter. 1981, 97,183.
[5]
Sanger,D. J. Behav. Pharmacol. 1995, 6,116.
[6]
(a) Hagmann,W. K. J. Med. Chem. 2008, 51,4359.
[6]
(b) Kirk,K. L. Org. Process Res. Dev. 2008, 12,305.
[6]
(c) Meanwell,N. A. J. Med. Chem. 2011, 54,2529.
[6]
(d) Wang, J.; Sa?nchez-Rosello?, M.; Acen?a, J.; Pozo, C.; Sorochinsky,A. E.; Fustero, S.; Soloshonok,V. A.; Liu, H. Chem. Rev. 2014, 114,2432.
[7]
Monir, K.; Bagdi,A. K.; Ghosh, M.; Hajra, A. J. Org. Chem. 2015, 80,1332.
[8]
Wu, Y.; Zhang,H. -R.; Jin,R. -X.; Lan, Q.; Wang,X. -S. Adv. Synth. Catal. 2016, 358,3528.
[9]
Wang,R. -N.; Wang,J. -C.; Tang,Q. -X.; Zhao, X.; Wang,J. -F.; Leng,Y. -T.; Wu,Y. -J.; Chang,J. -B.; Wu,Y. -S.; Zhang,Z. -D.; Wang,S. -W. Tetrahedron Lett. 2019, 60,586.
[10]
Ji,X. -M.; We, L.; Chen, F.; Tang,R. -Y. RSC Adv. 2015, 5,29766.
[11]
Chen,X. -Y.; Ding,L. -C.; Li,L. -L.; Li,J. -Y.; Zou,D. -P.; Wu,Y. -J.; Wu,Y. -S. Tetrahedron Lett. 2020, 61,151538.
[12]
Han,S. -J.; Gao,X. -Y.; Wu,Q. -S.; Li,J. -Y.; Zou,D. -P.; Wu,Y. -J.; Wu,Y. -J. Adv. Synth. Catal. 2016, 3361,1559.
[13]
Lefebvre, Q.; Hoffmann, N.; Rueping, M. Chem. Commun. 2016, 52,2493.
[14]
Zhou,Q. -G.; Xu, S.; Zhang,R. -H. Tetrahedron Lett. 2019, 60,734.
[15]
Mi, X.; Kong,Y. -F.; Yang,H. -X.; Zhang,J. -Y.; Pi, C.; Cui,X. -L. Eur. J. Org. Chem. 2020,1019.
[16]
Liu,Y. -F.; Ling,Y. -J.; Lu, L.; Shen, Q. Chin. J. Chem. 2021, 39,1667.
[17]
Electrophilic fluoroalkylating reagents based on sulfonium or selenium-ylide skeleton, see: (a) Liu,Y. -F.; Shao,X. -X.; Lu, L; Shen, Q. Org. Lett. 2015, 17,2752.
[17]
(b) Zhu,J. -S.; Liu,Y. -F.; Shen, Q. Angew. Chem.,Int. Ed. 2016, 55,9050.
[17]
(c) Liu,Y. -F.; Lu, L.; Shen, Q. Angew. Chem.,Int. Ed. 2017, 56,9930.
[17]
(d) Zhu,J. -S.; Zheng,H. -L.; Xue,X. -S.; Xiao,Y. -S.; Liu,Y. -F.; Shen, Q. Chin. J. Chem. 2018, 36,1069.
[17]
(e) Ge,H. -M.; Shen, Q. Org. Chem. Front. 2019, 6,2205.
[17]
(f) Liu,Y. -F.; Ge,H. -M.; Lu, L.; Shen, Q. Chin. J. Org. Chem. 2019, 39,257 (in Chinese).
[17]
( 刘亚飞, 葛航铭, 吕龙, 沈其龙, 有机化学, 2019, 39,257.)
[17]
(g) Hong, X.; Liu,Y. -F.; Lu, L.; Shen, Q. Chin. J. Chem. 2020, 38,1317.
[18]
Selected examples for phosphonium or sulfonium ylides in photoredox-catalyzed reactions: (a) Lu,L. -Q.; Li,T. -R.; Wang, Q.; Xiao,,W. -J. Chem. Soc. Rev. 2017, 46,4135.
[18]
(b) Das, M.; Vu,M. D.; Zhang, Q.; Liu,X. -W. Chem. Sci. 2019, 10,1687.
[18]
(c) Vu,M. D.; Leng,W. -L.; Hsu,H. -C.; Liu,X. -W. Asian J. Org. Chem. 2019, 8,93.
[18]
(d) Xia,X. -D.; Lu,L. -Q.; Liu,W. -Q.; Chen,D. -Z.; Zheng,Y. -H.; Wu,L. -Z.; Xiao,W. -J. Chem.-Eur. J. 2016, 22,8432.
[18]
(e) Yuan, F.; Yan,D. -M.; Gao,P. -P.; Shi,D. -Q.; Xiao,W. -J.; Chen,J. -R. ChemCatChem 2021, 12,543.
[19]
Related work for photo-trifluoromethylation via a donor-acceptor adduct, see: (a) Cheng,Y. -Z.; Yuan,X. -G.; Ma, J.; Yu,,S. -Y. Chem.- Eur. J. 2015, 21,8355.
[19]
(b) Macé, Y.; Pradet, C.; Popkin, M.; Blazejewski,J. -C.; Magnier, E. Tetrahedron Lett. 2010, 51,5388.
[20]
Pericherla, K.; Kaswan, P.; Khedara, P.; Khungara, B.; Parang, K.; Kumara, A. RSC Adv. 2013, 3,18923.
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