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ChemComm
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COMMUNICATION
Journal Name
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3
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photocatalyst (aizenuranine) is converted to excited dye*. A
single electron transfer between dye* and –SCN anion
generates dye radical anion (dye•-) and •SCN radical. Subseque-
ntly, molecular oxygen oxidizes dye•- back to its ground state
to finish the photocatalytic cycle. Meanwhile, O2 is reduced to
form O2•-. Then •SCN radical directly reacts with aldoximes
Cui and L. Q. Chen, J. Mater. Chem. A., 2016, 4, 10070.
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affording iminoxyl radical
O2 may also serve as the HAT agent and reacts with
aldoximes affording iminoxyl radical
I
and thiocyanic acid. In addition,
•-
- 14
I and HO2 . The
•
generated intermediate could further react with SCN radical
I
B. Yan, Y. Zhang and J. B. Wang, Adv. Synth. Catal., 2017, 359
4068.
,
to produce eneaminooxyl sulfanecarbonitrile II
.
The
abstraction of a proton from intermediate II by O2•- produces
4
5
6
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and L. Yu, Sci. Bull., 2019, doi: 10.1016/j.scib.2019.07.007.
For selected examples for the dehydration of aldoximes, see:
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285. (b) D. C. Barman, A. J. Thakur, D. Prajapati and J. S.
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Scheme 3 Proposed mechanism.
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2013, , 2560. (h) K. Tambaraa and G. D. Pantoş, Org. Biomol.
,
Conclusions
6
In conclusion, we have disclosed an effective catalytic
process for the dehydration of aldoximes by in-situ generated
•SCN radical under visible-light irradiation. The reaction is
highlighted by its cheap and easily available material, the easy
work-up procedure, excellent functional group tolerance and
generation of various aliphatic and aromatic nitriles in
moderate to excellent yields under mild reaction conditions.
Chem., 2013, 11, 2466. (i) M. F. Hartmer and S. R. Waldvogel,
Chem. Commun., 2015, 51, 16346. (j) D. L., Zhang, Y. P.
Huang, E. L. Zhang, R. Yi, C. Chen, L. Yu and Q. Xu, Adv. Synth.
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7
8
D. S. Bolotin, N. A. Bokach, M. Y. Demakova and V. Y.
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Chem., 2015, 17, 3515. (c) W. Zhang, J.-T. Guo, Y. Yu, Z. Guan
and Y.-H. He, Tetrahedron, 2018, 74, 3038.
9
Conflicts of interest
There are no conflicts to declare.
10 (a) P.-F. Yuan, Q.-B. Zhang, X.-L. Jin, W.-L. Lei, L.-Z. Wu and Q.
Liu, Green Chem., 2018, 20, 5464. (b) S. S. Shah and N. D. P.
Singh, Tetrahedron Lett., 2018, 59, 247.
Acknowledgements
11 For the generation of iminoxyl radical selected examples, see:
(a) B. Han, X.-L. Yang, R. Fang, W. Yu, C. Wang, X.-Y. Duan
and S. Liu, Angew. Chem. Int. Ed., 2012, 51, 8816. (b) X.-X.
Peng, Y.-J. Deng, X.-L. Yang, L. Zhang, W. Yu and B. Han, Org.
Lett., 2014, 16, 4650. (c) X.-L. Yang, F. Chen, N.-N. Zhou, W.
Yu and B. Han, Org. Lett., 2014, 16, 6476.
We are grateful for financial support from the NSFC (No.
21572090 and 21871123) and the Fundamental Research
Funds for the Central Universities (lzujbky-2017-k05).
12 (a) N. A. Romero and D. A. Nicewicz, Chem. Rev., 2016, 116
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Notes and references
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4 | J. Name., 2012, 00, 1-3
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