D
X. Tian et al.
Letter
Synlett
On the basis of the above results and previous reports in
the literature,11,24,25 a possible mechanism is proposed
(Scheme 4). The present stepwise reaction starts with oxi-
dation of the benzyl ether to give benzaldehyde under
catalysis by an active species from TEMPO/HNO3.24 Subse-
quently, it is possible that the resulting benzaldehyde reacts
with [NH3] from NH4OAc to form an imine intermediate.11,25
This is followed by the formation of the benzonitrile prod-
uct through oxydehydrogenation of the resulting imine.11,25
In conclusion, we have developed a direct method for
the conversion of benzyl ethers into aromatic nitriles by us-
ing NH4OAc as the nitrogen source and oxygen as the termi-
nal oxidant with catalysis by TEMPO/HNO3. Under the pres-
ent conditions, various benzyl ethers were smoothly con-
verted into aromatic nitriles in a low to high yields.
Preliminary mechanistic investigations suggested that the
present transformation involves a stepwise reaction in
which the oxidation of the benzyl methyl ether to a benzal-
dehyde is followed by conversion of the benzaldehyde into
an imine intermediate that can undergo oxydehydrogena-
tion to give the benzonitrile product. These results are valu-
able for both the synthesis of aromatic nitriles and for the
deprotection of ether-protected hydroxy groups to form
nitrile groups in multistep organic syntheses.
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Funding Information
The authors would like to thank the Program for Science and Technol-
ogy Innovation Talents in Universities of Henan Province (Grant
No.15HASTIT004) and the Open Project of State Key Laboratory for
Oxo Synthesis and Selective Oxidation (Grant No. OSSO-2015-21) for
financial support.()
(10) (a) Zhang, X.-L.; Liu, X.-L.; Sang, X.-Y.; Sheng, S.-R. Synth.
Commun. 2017, 47, 232. (b) Rapeyko, A.; Climent, M. J.; Corma,
A.; Concepción, P.; Iborra, S. ACS Catal. 2016, 6, 4564.
(c) Hartmer, M. F.; Waldvogel, S. R. Chem. Commun. 2015, 51,
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Supporting Information
Supporting information for this article is available online at
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© Georg Thieme Verlag Stuttgart · New York — Synlett 2018, 29, A–E