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In conclusion, we have developed the first organo-catalyzed
Michael addition of 2-fluoro-2-arylacetonitriles to activated alke-
nes, which allows an efficient synthesis of a variety of arylacetoni-
triles containing a fluorinated stereogenic center. This protocol
uses DBU as an organocatalyst and has a broad substrate scope:
a, b-unsaturated ketones, esters, nitriles and sulfones were all
proved to be competent. Besides, water proved to be a good solvent
for this addition reaction.
Declaration of Competing Interest
ˇ
´
bjoc.4.17; (n) M. Urban, M. Franc, M. Hofmanová, I. Císarová, J. Vesely, Org.
Biomol. Chem. 15 (2017) 9071–9076; (o) G.K. Prakash, F. Wang, T. Stewart, T.
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Zhang, Y. Zhang, Y. Ji, H. Li, W. Wang, Chem. Commun. 28 (2009) 4886–4888;
(q) T. Furukawa, N. Shibata, S. Mizuta, S. Nakamura, T. Toru, M. Shiro, Angew.
Chem., Int. Ed. Engl. 47 (2008) 8051–8054.
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
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Support of our work by the Natural Science Foundation of
Shanghai (16ZR1413800).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
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[12] Synthetic procedure: under an air atmosphere, catalyst DBU (225 mg,
1.48 mmol) was added to a reaction mixture of acrylonitrile 2m (7.4 mmol,
0.39 g) and 2-fluoro-2-phenylacetonitrile 1a (7.4 mmol, 1.0 g) in H2O (15 mL)
at 25 ℃. The reaction was reacted for 5 h, followed by extraction with ethyl
acetate (10 mL Â 3). The organic phase was dried over Na2SO4, filtered, and
concentrated under vacuum to give the crude 3am that was purified by flash
column chromatography using PE/EA (9:1) as an eluent to give the
corresponding 1,4-adduct in 85% yield (1.18 g). Light yellow liquid. 1H NMR
(500 MHz, CDCl3) d 7.53 (s, 5H), 2.83–2.43 (m, 4H). 19F NMR (376 MHz,
CDCl3) d À150.71 (s). 13C NMR (126 MHz, CDCl3) d 134.1 (d, J = 22.5 Hz),
130.7, 129.4, 124.4 (d, J = 6.3 Hz), 117.2, 115.9 (d, J = 33.9 Hz), 90.1 (d, J = 186.9
Hz), 37.2 (d, J = 25.9 Hz), 12.5 (d, J = 4.3 Hz). IR (neat) 3070, 2968, 2254, 2210,
1452, 1225, 761, 691 cmÀ1. HRMS (ESI): Calcd for (C11H9FN2Na) ([M+Na]+)
211.0642; found: 211.0647.
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