Citation: Qing-Wen Gui, Fan Teng, Zhou-Chao Li, Zhi-Yuan Xiong, Xue-Feng Jin, Ying-Wu Lin, Zhong Cao, Wei-Min He. Visible-light-initiated tandem synthesis of difluoromethylated oxindoles in 2-MeTHF under additive-, metal catalyst-, external photosensitizer-free and mild conditions[J]. Chinese Chemical Letters, ;2021, 32(6): 1907-1910. doi: 10.1016/j.cclet.2021.01.021 shu

Visible-light-initiated tandem synthesis of difluoromethylated oxindoles in 2-MeTHF under additive-, metal catalyst-, external photosensitizer-free and mild conditions

a.
College of Chemistry and Materials Science, Hunan Agricultural University, Changsha 410128, China
b.
School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, China
c.
Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation, Changsha University of Science and Technology, Changsha 410114, China

weiminhe2016@yeah.net

Received Date: 25 November 2020
Revised Date: 12 January 2021
Accepted Date: 12 January 2021
Available Online: 15 January 2021

Figures(6)

An efficient and eco-friendly protocol for synthesizing difluoromethylated oxindoles through a visible-light induced one-pot tandem reaction of N-arylacrylamides, difluoroacetic acid and PhI(OAc)₂ was developed. This reaction proceeded in the absence of any additive, base, metal-catalyst and external photosensitizer, using cheap and easily available CHF₂CO₂H as the difluoromethylation reagent and bulk biomass-derived 2-MeTHF as the sole solvent. 26 Examples of N-arylacrylamide substrates were investigated, and all of them successfully underwent difluoromethylation to deliver the target products in good to excellent yields.
- Green chemistry,
- Visible light,
- External photosensitizer-free,
- Tandem reaction,
- 2-MeTHF
1. [1]
  (a) Z. Cao, Q. Zhu, Y.W. Lin, W.M. He, Chin. Chem. Lett. 30 (2019) 2132-2138;
  (b) Y. Kim, C.J. Li, Green Synth. Catal. 1 (2020) 1-11.
2. [2]
  (a) C.J. Clarke, W.C. Tu, O. Levers, A. Bröhl, J.P. Hallett, Chem. Rev. 118 (2018) 747-800;
  (b) M. Li, F. Wu, Y. Gu, Chin. J. Catal. 40 (2019) 1135-1140;
  (c) L.H. Lu, Z. Wang, W. Xia, et al., Chin. Chem. Lett. 30 (2019) 1237-1240;
  (d) S. Peng, Y.X. Song, J.Y. He, et al., Chin. Chem. Lett. 30 (2019) 2287-2290;
  (e) Q. Sun, L. Liu, Y. Yang, Z. Zha, Z. Wang, Chin. Chem. Lett. 30 (2019) 1379-1382;
  (f) F. Gao, R. Bai, F. Ferlin, et al., Green Chem. 22 (2020) 6240-6257;
  (g) F.H. Qin, X.J. Huang, Y. Liu, et al., Chin. Chem. Lett. 31 (2020) 3267-3270.
3. [3]
  (a) Q. Zhen, L. Chen, L. Qi, et al., Chem. Asian J. 15 (2020) 106-111;
  (b) W.H. Bao, Z. Wang, X. Tang, et al., Chin. Chem. Lett. 30 (2019) 2259-2262;
  (c) Y. Wang, J. Shen, Q. Chen, L. Wang, M. He, Chin. Chem. Lett. 30 (2019) 409-412.
4. [4]
  (a) F. Wang, T.Q. Wei, P. Xu, S.Y. Wang, S.J. Ji, Chin. Chem. Lett. 30 (2019) 379-382;
  (b) Y. Zhang, K. Sun, Q. Lv, et al., Chin. Chem. Lett. 30 (2019) 1361-1368;
  (c) J. Chen, L. Wu, J. Wu, Chin. Chem. Lett. 31 (2020) 2993-2995;
  (d) F.S. He, Y. Yao, W. Xie, J. Wu, Chem. Commun. 56 (2020) 9469-9472;
  (e) Q.W. Gui, F. Teng, S.N. Ying, et al., Chin. Chem. Lett. 31 (2020) 3241-3244.
5. [5]
  (a) X. Mi, Y. Kong, J. Zhang, C. Pi, X. Cui, Chin. Chem. Lett. 30 (2019) 2295-2298;
  (b) D.Q. Dong, L.X. Li, G.H. Li, et al., Chin. J. Catal. 40 (2019) 1494-1498;
  (c) M. Fu, X. Ji, Y. Li, G.J. Deng, H. Huang, Green Chem. 22 (2020) 5594-5598;
  (d) L. Lu, Y. Li, X. Jiang, Green Chem. 22 (2020) 5989-5994;
  (e) F.S. He, S. Xie, Y. Yao, J. Wu, Chin. Chem. Lett. 31 (2020) 3065-3072;
  (f) L. Zou, L. Wang, L. Sun, X. Xie, P. Li, Chem. Commun. 56 (2020) 7933-7936;
  (g) S. He, X. Chen, F. Zeng, et al., Chin. Chem. Lett. 31 (2020) 1863-1867;
  (h) W. Xiao, J. Wu, Chin. Chem. Lett. 31 (2020) 3083-3094;
  (i) P. Wang, Q. Zhao, W. Xiao, J. Chen, Green Synth. Catal. 1 (2020) 42-51.
6. [6]
  (a) Y. Liu, X.L. Chen, K. Sun, et al., Org. Lett. 21 (2019) 4019-4024;
  (b) Q. Liu, L. Wang, H. Yue, et al., Green Chem. 21 (2019) 1609-1613;
  (c) J. Shi, W. Wei, Chin. J. Org. Chem. 40 (2020) 2170-2172;
  (d) Z. Gan, G. Li, X. Yang, et al., Sci. China Chem. 63 (2020) 1652;
  (e) L.Y. Xie, Y.S. Bai, X.Q. Xu, et al., Green Chem. 22 (2020) 1720-1725;
  (f) J. Xu, H. Zhang, J. Zhao, et al., Org. Chem. Front. 7 (2020) 4031-4042;
  (g) W.B. He, L.Q. Gao, X.J. Chen, et al., Chin. Chem. Lett. 31 (2020) 1895-1898.
7. [7]
  (a) J. Bergman, Oxindoles, in: E.F.V. Scriven, C.A. Ramsden (Eds.), Advances in Heterocyclic Chemistry, Vol. 117, Academic Press, 2015, pp. 1-81;
  (b) N. Ye, H. Chen, E.A. Wold, P.Y. Shi, J. Zhou, ACS Infect. Dis. 2 (2016) 382-392;
  (c) M.Z. Zhang, L. Liu, Q. Gou, et al., Green Chem. 22 (2020) 8369-8374;
  (d) Y. An, Y. Li, J. Wu, Org. Chem. Front. 3 (2016) 570-573;
  (e) C. Wang, Q. Chen, Q. Guo, et al., J. Org. Chem. 81 (2016) 5782-5788;
  (f) K. Zhou, J. Chen, J. Wu, Chin. Chem. Lett. 31 (2020) 2996-2998.
8. [8]
  (a) Z.Z. Han, C.P. Zhang, Adv. Synth. Catal. 362 (2020) 4256-4292;
  (b) A. Lemos, C. Lemaire, A. Luxen, Adv. Synth. Catal. 361 (2019) 1500-1537;
  (c) W. Sha, W. Zhang, S. Ni, et al., J. Org. Chem. 82 (2017) 9824-9831; (d) Y. Zhou, Z. Xiong, J. Qiu, L. Kong, G. Zhu, Org. Chem. Front. 6 (2019) 1022-1026;
  (e) C.F. Meyer, S.M. Hell, A. Misale, A.A. Trabanco, V. Gouverneur, Angew. Chem. Int. Ed. 58 (2019) 8829-8833;
  (f) R. Xu, C. Cai, Chem. Commun. 55 (2019) 4383-4386;
  (g) D. Zhang, Z. Fang, J. Cai, et al., Chem. Commun. 56 (2020) 8119-8122;
  (h) D.Q. Dong, H. Yang, J.L. Shi, et al., Org. Chem. Front. 7 (2020) 2538-2575.
9. [9]
  (a) Y. Xiang, Y. Li, Y. Kuang, J. Wu, Chem. Eur. J. 23 (2017) 1032-1035;
  (b) J.Y. Wang, Y.M. Su, F. Yin, et al., Chem. Commun. 50 (2014) 4108-4111;
  (c) J.Y. Wang, X. Zhang, Y. Bao, et al., Org. Biomol. Chem. 12 (2014) 5582-5585.
10. [10]
  J. Liu, S. Zhuang, Q. Gui, et al., Eur. J. Org. Chem. (2014) 3196-3202.
11. [11]
  X.J. Tang, C.S. Thomoson, W.R. Dolbier, Org. Lett. 16(2014) 4594-4597. doi: 10.1021/ol502163f
12. [12]
  H. Sun, Y. Jiang, Y.S. Yang, et al., Org. Biomol. Chem. 17(2019) 6629-6638. doi: 10.1039/C9OB01213C
13. [13]
  P. Xiong, H.H. Xu, J. Song, H.C. Xu, J. Am. Chem. Soc. 140(2018) 2460-2464. doi: 10.1021/jacs.8b00391
14. [14]
  Z. Ruan, Z. Huang, Z. Xu, et al., Org. Lett. 21(2019) 1237-1240. doi: 10.1021/acs.orglett.9b00361
15. [15]
  (a) L.Y. Xie, S. Peng, T.G. Fan, et al., Sci. China Chem. 62 (2019) 460-464;
  (b) W.M. He, Y.W. Lin, D.H. Yu, Sci. China Chem. 63 (2020) 291-293;
  (c) L.Y. Xie, T.G. Fang, J.X. Tan, et al., Green Chem. 21 (2019) 3858-3863;
  (d) K.J. Liu, T.Y. Zeng, J.L. Zeng, et al., Chin. Chem. Lett. 30 (2019) 2304-2308;
  (e) K.J. Liu, J.H. Deng, T.Y. Zeng, et al., Chin. Chem. Lett. 31 (2020) 1868-1872;
  (f) Y. Wu, W. He, Chin. J. Org. Chem. 40 (2020) 2597-2599;
  (g) L.Y. Xie, Y.S. Liu, H.R. Ding, et al., Chin. J. Catal. 41 (2020) 1168-1173;
  (h) J.Y. Chen, C.T. Zhong, Q.W. Gui, et al., Chin. Chem. Lett. 32 (2021) 475-479;
  (i) W.T. Wei, Q. Li, M.Z. Zhang, W.M. He, Chin. J. Catal. 42 (2021) 731-742.
16. [16]
  R. Sakamoto, H. Kashiwagi, K. Maruoka, Org. Lett. 19(2017) 5126-5129. doi: 10.1021/acs.orglett.7b02416
17. [17]
  (a) Y. Mei, L. Zhao, Q. Liu, et al., Green Chem. 22 (2020) 2270-2278;
  (b) D. Xia, Y. Li, T. Miao, P. Li, L. Wang, Green Chem. 19 (2017) 1732-1739.
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