10.1002/adsc.201701047
Advanced Synthesis & Catalysis
hydrobromic acid (HBr) and hydrochloric acid (HCl)
provide the desired product in low yields (see the
Supporting Information).
Acknowledgements
J. K. acknowledges Max-Planck Society-Germany
and DST-India (DST/INT/MPG/P-09/2016) for
financial support through Indo-Max Planck partner
group project. J. K. also gratefully acknowledges
DST-SERB India for young scientist start-up research
grant (YSS/2014/000236). P.
C
and S.
G
acknowledge IIT (BHU) for a research fellowship. J.
K thanks to Dr K. Murugan and Mr. Albert Pape for a
helpful discussion during the manuscript preparation.
J. K acknowledges Central Instrumentation Facility
Center (CIFC)-IIT BHU for the NMR facilities. S. S
and P. S acknowledge Pondicherry University for
MASS facilities. P. S acknowledges CSIR for senior
research fellowship (SRF).
Scheme 8. Proposed mechanism for the denitrosation
reaction.
REFERENCES
[1] a) J.-P. Anselme, The organic chemistry of N-
nitrosamines: A brief review, ACS, Washington, DC,
1979; b) R. N. Loeppky, C. J. Michejda, Nitrosamines
and Related N-Nitroso Compounds: Chemistry and
Biochemistry; ACS, Washington, DC 1994; c) R. N.
Loeppky, J. R. Outram, N-Nitroso Compounds:
Occurrence and Biological Effects; IARC Scientific
Publishers: Lyon, 1982.
[2] a) D. L. Browne and J. P. A. Harrity, Tetrahedron
2010, 66, 553-568; b) P. Chaudhary, S. Gupta, P.
Sureshbabu, S. Sabiah, J. Kandasamy, Green. Chem.
2016, 18, 6215- 6221; c) R. L. Hinmap and K. L.
Hamm, J. Org. Chem, 1958, 23, 529-531; d) F. W.
Schueler, C. Hanna, J. Am. Chem. Soc. 1951, 73,
4996; e) F. H. C. Stewart, Chem. Rev. 1964, 64, 129-
147.
[3] a) D. Seebach, D. Enders, Angew. Chem., Int. Ed.
Engl. 1975, 14, 15-32; b) L. K. Keefer, C. H. Fodor,
J. Am. Chem. Soc. 1970, 92, 5747-5748; c) B. Liu, Y.
Fan, Y. Gao, C. Sun, C. Xu, J. Zhu, J. Am. Chem. Soc.
2013, 135, 468-473; d) J. Chen, P. Chen, C. Song, J.
Zhu, Chem. Eur. J. 2014, 20, 14245-14249; e) J. W.
Dong, Z. J. Wu, Z. Y. Liu, P. Liu, P. P. Sun, J. Org.
Chem. 2015, 80, 12588- 12593; f) T. Gao, P. Sun, J.
Org. Chem. 2014, 79, 9888- 9893; g) D. D. Li, Y. X.
Cao, G. W. Wang, Org. Biomol. Chem. 2015, 13,
6958-6964; h) J. Wang, M. Wang, K. Chen, S. Zha, C.
Song, J. Zhu, Org. Lett. 2016, 18, 1178-1181; i) B.
Liu, C. Song, C. Sun, S. Zhou, J. Zhu, J. Am. Chem.
Soc. 2013, 135, 16625-16631; j) Y. N. Wu, L.-J. Feng,
X. Lu, F. Y. Kwong, H.-B. Luo, Chem. Commun.
2014, 50, 15352-15354; k) Y. Wu, L. Sun, Y. Chen, Q.
Zhou, J.-W. Huang, H. Miao, H.-B. Luo, J. Org.
Chem. 2016, 81, 1244-1250; l) F. Xie, Z. Qi, S. Yu, X.
Li, J. Am. Chem. Soc. 2014, 136, 4780-4787.
Scheme 9. Denitrosation reaction catalyzed by hydroiodic
acid.
In summary, we have developed an efficient and
practical method for the denitrosation of N-
nitrosamines using iodine and triethylsilane. The
reaction proceeds at room temperature in a short span
of time and provides typical yields of 85-97%.
Reduction susceptible functionalities such as alkene,
alkyne, nitrile, nitro, aldehyde, ketone and ester were
found to be stable under the standard reaction
conditions. Applications of the current methodology
were demonstrated in different multistep organic
synthesis. In addition, the nitroso moiety was
explored as a protecting group for secondary amines.
Overall we found the current methodology will have a
wide of scope in organic synthesis.
Experimental Section
General Experimental procedure for the
denitrosation of N-nitrosamines
N-nitrosamine (1.0 mmol, 1.0 equiv.) was allowed to
stir in dichloromethane (3 mL) approximately for 2
min at room temperature to which iodine (76 mg, 0.3
equiv.) and triethylsilane (0.24 mL, 1.5 equiv.) was
added. The reaction was further allowed to stir for 10-
15 minutes and the progress of the reaction was
monitored by TLC. After completion, the reaction
mixture was quenched with saturated solution of
sodium thiosulfate (20 mL) extracted with ethyl
acetate (2 x 25 mL). The organic layer was dried over
anhydrous sodium sulfate, concentrated and subjected
for column chromatography (SiO2, eluent:
Hexane/ethyl acetate) to obtain corresponding pure
substituted secondary amines.
[4] a) E. L. Teuten, R. N. Loeppky, Org. Biomol.
Chem. 2005, 3, 1097-1108; b) J. Zhang, J. Jiang, Y.
Li, X. Wan, J. Org. Chem. 2013, 78, 11366-11372; c)
R. N. Leoppky, W. Tomasik, J. Org. Chem. 1983, 48,
2751-2757.
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