Organic Letters
Letter
Fustero, S.; Soloshonok, V. A.; Liu, H. Chem. Rev. 2014, 114, 2432.
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dihydrobenzofuran 8p was not detected, which was similar to
the result of 3a obtained in Table 1.
In summary, we have demonstrated a convenient and
versatile intramolecular trifluoromethylacylation and -arylation
of alkenes by use of stable and inexpensive CF3SO2Na as the
trifluoromethylation reagent and K2S2O8 as the oxidant via a
free-radical process. This method affords facile and accurate
access to a range of chroman-4-ones and chromanes in
moderate to good yields with excellent chemoselectivity.
Control experiments and DFT calculations suggest that the
triggered transformation for the construction of ·CF3 is
embodied in the rate-determining step and subsequent free-
radical addition, cyclization, and oxidation can efficiently take
place in the presence of K2S2O8. Prominent advantages
indicate that this difunctionalization reaction can be readily
performed in aqueous media under mild conditions without a
transition metal catalyst. Further exploration of a green
synthetic method, especially in aqueous media, is ongoing in
our laboratory.
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ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
General experimental procedures, computational details,
1
characterization data and copies of H, 13C, and 19F
NMR spectra of products (PDF)
AUTHOR INFORMATION
Corresponding Authors
■
(7) (a) Li, Z.-L.; Li, X.-H.; Wang, N.; Yang, N.-Y.; Liu, X.-Y. Angew.
Chem., Int. Ed. 2016, 55, 15100. (b) Liu, Z.; Bai, Y.; Zhang, J.; Yu, Y.;
Tan, Z.; Zhu, G. Chem. Commun. 2017, 53, 6440.
(8) (a) Egami, H.; Kawamura, S.; Miyazaki, A.; Sodeoka, M. Angew.
Chem., Int. Ed. 2013, 52, 7841. (b) Lin, J.-S.; Xiong, Y.-P.; Ma, C.-L.;
Zhao, L.-J.; Tan, B.; Liu, X.-Y. Chem. - Eur. J. 2014, 20, 1332.
(c) Dagousset, G.; Carboni, A.; Magnier, E.; Masson, G. Org. Lett.
2014, 16, 4340. (d) Yasu, Y.; Koike, T.; Akita, M. Org. Lett. 2013, 15,
2136. (e) Chang, B.; Su, Y.; Huang, D.; Wang, K.-H.; Zhang, W.; Shi,
Y.; Zhang, X.; Hu, Y. J. Org. Chem. 2018, 83, 4365.
ORCID
Notes
The authors declare no competing financial interest.
(9) (a) Carboni, A.; Dagousset, G.; Magnier, E.; Masson, G. Org.
Lett. 2014, 16, 1240. (b) Yasu, Y.; Koike, T.; Akita, M. Angew. Chem.,
Int. Ed. 2012, 51, 9567. (c) Jiang, X.-Y.; Qing, F.-L. Angew. Chem., Int.
Ed. 2013, 52, 14177. (d) Egami, H.; Shimizu, R.; Sodeoka, M.
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Chem. Soc. 2012, 134, 12462. (f) Deng, Q.-H.; Chen, J.-R.; Wei, Q.;
Zhao, Q.-Q.; Lu, L.-Q.; Xiao, W.-J. Chem. Commun. 2015, 51, 3537.
ACKNOWLEDGMENTS
■
This work was supported by the National Natural Science
Foundation of China (21602190, 21803050), the Foundation
of Department of Science and Technology of Henan Province
(172102210456), the Foundation of Department of Education
of Henan Province (17A150049), and the Nanhu Scholars
Program for Young Scholars of XYNU.
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