Organic Letters
Letter
1172. (c) Sweeney, J. B. Chem. Soc. Rev. 2002, 31, 247. (d) Muller, P.;
Fruit, C. Chem. Rev. 2003, 103, 2905.
(2) Minakata, S.; Takeda, Y.; Kiyokawa, K. In Methods and Applications
of Cycloaddition Reaction in Organic Syntheses; Nishiwaki, N., Ed.; Wiley-
VCH: Weinheim, Chapter 2.
̈
Scheme 4. Proposed Mechanism for the Iodide-Mediated
Electrochemical Synthesis of Aziridines
(3) For reviews and highlights, see: (a) Singh, G. S.; D’hooghe, M.; De
Kimpe, N. Chem. Rev. 2007, 107, 2080. (b) Jung, N.; Brase, S. Angew.
̈
Chem., Int. Ed. 2012, 51, 5538.
(4) (a) Ando, T.; Kano, D.; Minakata, S.; Ryu, I.; Komatsu, M.
Tetrahedron 1998, 54, 13485. (b) Mansuy, D.; Mahy, J. P.; Dureault, A.;
Bedi, G.; Battioni, P. J. Chem. Soc., Chem. Commun. 1984, 1161.
(5) Jain, S. L.; Sharma, B. B.; Sain, B. Tetrahedron Lett. 2004, 45, 8731.
(6) Jeong, J. U.; Tao, B.; Sagasser, I.; Henniges, H.; Sharpless, K. B. J.
Am. Chem. Soc. 1998, 120, 6844.
(7) (a) Minakata, S.; Morino, Y.; Oderaotoshi, Y.; Komatsu, M. Chem.
Commun. 2006, 3337. (b) Minakata, S.; Morino, Y.; Ide, T.;
Oderaotoshi, Y.; Komatsu, M. Chem. Commun. 2007, 3279.
(8) (a) Li, J. Y.; Liang, J. L.; Chan, P. W. H.; Che, C. M. Tetrahedron
Lett. 2004, 45, 2685. (b) Li, J. Y.; Chan, P. W. H.; Che, C. M. Org. Lett.
2005, 7, 5801. (c) Krasnova, L. B.; Hili, R. M.; Chernoloz, O. V.; Yudin,
A. K. ARKIVOC 2005, (iv), 26. (d) Krasova, L. B.; Yudin, A. K. Org. Lett.
2006, 8, 2011. (e) Richardson, R. D.; Desaize, M.; Wirth, T. Chem.
Eur. J. 2007, 13, 6745.
(9) (a) Uyanik, M.; Okamoto, T.; Yasui, T.; Ishihara, K. Science 2010,
328, 1376. (b) Uyanik, M.; Suzuki, D.; Yasui, T.; Ishihara, K. Angew.
Chem., Int. Ed. 2011, 50, 5331.
(10) Yoshimura, A.; Middleton, K. R.; Zhu, C. J.; Nemykin, V. N.;
Zhdankin, V. V. Angew. Chem., Int. Ed. 2012, 51, 8059.
iodide is regenerated and re-enters the catalytic cycle. Since it is
easier to form an iodine radical by oxidation of iodide than it is to
form a bromine radical via oxidation of bromide, better results are
anticipated when iodide ion containing mediators are used.
In conclusion, we have developed an efficient electrochemical
strategy for the catalytic aziridination of alkenes. The electro-
chemical synthesis was performed under constant current
conditions in a simple undivided cell using a catalytic amount
of n-Bu4NI as a redox catalyst and CF3CH2OH as the solvent.
Additional supporting electrolyte is not required. A wide range of
functional groups proved to be compatible with the catalytic
system. Control experiments revealed that the electrocatalytic
aziridination most likely proceeds via a radical mechanism, rather
than through the intermediacy of a nitrene. The results further
demonstrate that electrochemically generated reactive halide
species constitute versatile reagents in organic synthesis. The
application of this chemistry to other chemical transformations is
underway in our laboratory.
(11) Varszegi, C.; Ernst, M.; van Laar, F.; Sels, B. F.; Schwab, E.; De
Vos, D. E. Angew. Chem., Int. Ed. 2008, 47, 1477.
(12) (a) Siu, T.; Yudin, A. K. J. Am. Chem. Soc. 2002, 124, 530. (b) Siu,
T.; Picard, C. J.; Yudin, A. K. J. Org. Chem. 2005, 70, 932.
(13) (a) Zhang, N. T.; Zeng, C. C.; Lam, C. M.; Grur, R. K.; Little, R. D.
J. Org. Chem. 2013, 78, 2104. (b) Zeng, C. C.; Zhang, N. T.; Lam, C. M.;
Little, R. D. Org. Lett. 2012, 14, 1314. (c) Francke, R.; Little, R. D. J. Am.
Chem. Soc. 2014, 136, 427.
(14) (a) Li, W. C.; Zeng, C. C.; Hu, L. M.; Tian, H. Y.; Little, R. D. Adv.
Synth. Catal. 2013, 355, 2884. (b) Gao, W. J.; Li, W. C.; Zeng, C. C.;
Tian, H. Y.; Hu, L. M.; Little, R. D. J. Org. Chem. 2015, 80, 781.
(15) Yoo, S. J.; Li, L. J.; Zeng, C. C.; Little, R. D. Angew. Chem., Int. Ed.
2014, DOI: 10.1002/anie.201410207.
ASSOCIATED CONTENT
* Supporting Information
(16) Kiyokawa, K.; Kosaka, T.; Minakata, S. Org. Lett. 2013, 15, 4858.
(17) (a) Gardner, J. M.; Abrahamsson, M.; Farnum, B. H.; Meyer, G. J.
J. Am. Chem. Soc. 2009, 131, 16206. (b) Boschloo, G.; Hagfeldt, A. Acc.
Chem. Res. 2009, 42, 1819.
■
S
Conditions optimization, experimental details, and spectral data.
This material is available free of charge via the Internet at http://
AUTHOR INFORMATION
Corresponding Authors
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by grants from the National Natural
Science Foundation of China (Nos. 21272021 and 21472011)
and the National Key Technology R&D Program
(2011BAD23B01). Z.C.C. and R.D.L. are grateful to the US
National Science Foundation supported PIRE-ECCI (OISE-
0968399) and CenSURF Programs for fostering our interna-
tional collaboration.
REFERENCES
■
(1) (a) Aziridines and epoxides in Organic Synthesis; Yudin, A. K., Ed.;
Wiley-VCH: Weinheim, 2006. (b) Minakata, S. Acc. Chem. Res. 2009, 42,
D
Org. Lett. XXXX, XXX, XXX−XXX