Paper
Catalysis Science & Technology
Conclusions
C. Ni, M. Hu and J. Hu, Chem. Rev., 2015, 115, 765; (e) C. Ni
and J. Hu, Chem. Soc. Rev., 2016, 45, 5441; ( f ) H.-X. Song,
Q.-Y. Han, C.-L. Zhao and C.-P. Zhang, Green Chem., 2018, 20,
1662; (g) A. D. Dilman and V. V. Levin, Acc. Chem. Res.,
2018, 51, 1271.
In conclusion, we have studied the visible-light photoredox
catalysis for the preparation of perfluoroalkyl amides and
esters from low-cost and readily available perfluoroalkyl
halides. These reactions gave moderate to high yields for
amides and moderate yields for esters. The roles of different
reagents and photocatalysts as well as their impacts on these
reactions have been studied. The results show the
importance of the excited-state redox potentials on the
performance of the photocatalysts. To facilitate the oxidative
quenching of the perfluoroalkyl halides, the excited states
must possess sufficient redox potentials to reduce the
perfluoroalkyl halides. Among the four photocatalysts tested
in this work, only fac-[Ir(ppy)3] would have sufficient potential
to activate perfluoroalkyl bromide. On the other hand,
photocatalysts with highly-oxidizing excited states are
unfavourable for these reactions because the excited states
would be competed by non-productive reductive quenching.
Therefore, excited-state redox potentials are crucial factors
affecting the performance of these photocatalysts. The
mechanisms of these photocatalytic reactions have also been
proposed and examined by DFT calculation.
3 (a) J.-A. Ma and D. Cahard, Chem. Rev., 2008, 108, PR1; (b)
C.-P. Zhang, Q.-Y. Chen, Y. Guo, J.-C. Xiao and Y.-C. Gu,
Chem. Soc. Rev., 2012, 41, 4536; (c) S. Barata-Vallejo, B.
Lantaño and A. Postigo, Chem. – Eur. J., 2014, 20, 16806; (d) S.
Barata-Vallejo, S. M. Bonesi and A. Postigo, Org. Biomol.
Chem., 2015, 13, 11153; (e) B. Lantaño and A. Postigo, Org.
Biomol. Chem., 2017, 15, 9954; ( f ) Z. Feng, Y.-L. Xiao and X.
Zhang, Acc. Chem. Res., 2018, 51, 2264; (g) X. Zhu, J. Han, J.
Wang, N. Shibata, M. Sodeoka, V. A. Soloshonok, J. A. S.
Coelho and F. D. Toste, Chem. Rev., 2018, 118, 3887; (h) P.
Xiao, C. Ni, W. Miao, M. Zhou, J. Hu, D. Chen and J. Hu,
J. Org. Chem., 2019, 84, 8345.
4 (a) G. G. Furin, Russ. Chem. Rev., 2000, 69, 491; (b) N. O.
Brace, J. Fluorine Chem., 2001, 108, 147; (c) Q. Qi, Q. Shen and
L. Lu, J. Am. Chem. Soc., 2012, 134, 6548; (d) S. Barata-Vallejo
and A. Postigo, Coord. Chem. Rev., 2013, 257, 3051; (e) T.
Chatterjee, N. Iqbal, Y. You and E. J. Cho, Acc. Chem. Res.,
2016, 49, 2284; ( f ) X. Chen, Z. Tan, Q. Gui, L. Hu, J. Liu, J.
Wu and G. Wang, Chem. – Eur. J., 2016, 22, 6218; (g) J. J.
Douglas, M. J. Sevrin and C. R. J. Stephenson, Org. Process
Res. Dev., 2016, 20, 1134; (h) Q. Guo, M. Wang, Y. Wang, Z. Xu
and R. Wang, Chem. Commun., 2017, 53, 12317; (i) Y. Wang, J.
Wang, G.-X. Li, G. He and G. Chen, Org. Lett., 2017, 19, 1442;
( j) V. I. Supranovich, V. V. Levin, M. I. Struchkova and A. D.
Dilman, Org. Lett., 2018, 20, 840; (k) S. Barata-Vallejo, M. V.
Cooke and A. Postigo, ACS Catal., 2018, 8, 7287; (l) Y. Huang,
Y.-Y. Lei, L. Zhao, J. Gu, Q. Yao, Z. Wang, X.-F. Li, X. Zhang
and C.-Y. He, Chem. Commun., 2018, 54, 13662.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work has been supported by a General Research Fund
(Project No. CityU 11306217) from the Research Grants
Council of the Hong Kong SAR, China. Y. Xiao and R. Liu
acknowledge the receipt of
a University Postgraduate
5 (a) D. A. Nagib, M. E. Scott and D. W. C. MacMillan, J. Am.
Chem. Soc., 2009, 131, 10875; (b) P. V. Pham, D. A. Nagib and
D. W. C. MacMillan, Angew. Chem., Int. Ed., 2011, 50, 6119; (c)
C.-J. Wallentin, J. D. Nguyen, P. Finkbeiner and C. R. J.
Stephenson, J. Am. Chem. Soc., 2012, 134, 8875; (d) N. Iqbal, J.
Jung, S. Park and E. J. Cho, Angew. Chem., Int. Ed., 2014, 53,
539; (e) N. J. W. Straathof, H. P. L. Gemoets, X. Wang, J. C.
Schouten, V. Hessel and T. Noël, ChemSusChem, 2014, 7,
1612; ( f ) E. J. Cho, Chem. Rev., 2016, 16, 47; (g) M. Daniel, G.
Dagousset, P. Diter, P.-A. Klein, B. Tuccio, A.-M. Goncalves, G.
Masson and E. Magnier, Angew. Chem., Int. Ed., 2017, 56,
3997; (h) S. Tang, L. Yin, Y.-L. Deng, Z.-Z. Li, L.-N. Wang, G.-X.
Huang and R.-L. Sheng, Tetrahedron Lett., 2017, 58, 329.
6 S. Y. Chow, M. Y. Stevens, S. Bergman and L. R. Odell, Chem.
– Eur. J., 2016, 22, 9155.
Studentship administered by City University of Hong Kong
(CityU). Prof. V. W.-W. Yam and Dr. A. K.-W. Chan from the
Department of Chemistry of the University of Hong Kong
(HKU) are acknowledged for the HRMS measurements.
Notes and references
1 (a) D. T. W. Chu, Organofluorine compounds in Medicinal
Chemistry and Biomedicine Applications, ed. R. Filler, Y.
Kobayashi and L. M. Yagupolskii, Elsevier, Amsterdam, 1993,
p. 165; (b) T. Hiyama and H. Yamamoto, Biologically Active
Organofluorine Compounds and Fluorine-Containing Materials,
ed. H. Yamamoto, Springer, Berlin, Herdelberg, New York,
2000, p. 137; (c) P. Kirsch, Modern Fluoroorganic Chemistry:
Synthesis, reactivity, Applications, Wiley-VCH, Weinheim, 2006;
(d) J. P. Bégué and D. Bonnet-Delpon, Bioorganic and
Medicinal Chemistry of Fluorine, Wiley, Hoboken, New Jersey
and Canada, 2008; (e) R. Berger, G. Resnati, P. Metrangolo, E.
Weber and J. Hulliger, Chem. Soc. Rev., 2011, 40, 3496; ( f )
N. A. Meanwell, J. Med. Chem., 2018, 61, 5822.
7 C.-O. Ng, H. Feng, S.-C. Cheng, Y. Xiao, L. T.-L. Lo and C.-C.
Ko, Asian J. Org. Chem., 2018, 7, 1587.
8 (a) M. H. Shaw, J. Twilton and D. W. C. MacMillan, J. Org.
Chem., 2016, 81, 6898; (b) V. Kais, Dissertation, University of
Regenburg, Regenburg, 2015, ch. 1, p. 3; (c) T. Hofbeck and
H. Yersin, Inorg. Chem., 2010, 49, 9290; (d) C.-C. Ko, L. T.-L.
Lo, C.-O. Ng and S.-M. Yiu, Chem. – Eur. J., 2010, 16, 13773;
(e) H. J. Bolink, E. Coronado, R. D. Costa, N. Lardiés and
2 (a) G. K. S. Prakash and A. K. Yudin, Chem. Rev., 1997, 97,
757; (b) J.-A. Ma and D. Cahard, Chem. Rev., 2004, 104, 6119;
(c) Y. Macé and E. Magnier, Eur. J. Org. Chem., 2012, 2479; (d)
Catal. Sci. Technol.
This journal is © The Royal Society of Chemistry 2020