Communication
ChemComm
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toluene as dppf was replaced with dcype, and a new product
was formed as clearly confirmed by the 31P NMR spectrum. Two
doublets appeared at 59.6 ppm and 52.9 ppm from the 31P NMR
spectrum suggesting two types of phosphorus environment.
After work-up, an orange solid was isolated, which was expected
to be the oxidative addition product via Ni(0) insertion to the
C–CN bond. However, single crystal analysis through X-ray
diffraction revealed a Z2-coordination of nickel to the double
bond of the phenyl ring adjacent to the CN group (Scheme 4,
complex I). Similar structures have been declared by Jones and
coworkers in the reaction with cyanoquinoline and Ni(dippe),
which ultimately undergoes C–CN oxidative addition.28
The effort to break the C–CN bond of complex I failed. Mean-
while, complex I reacted with EtOH in the presence of KHMDS
leading to the formation of 2c in 79% yield (eqn (5)). With
complex I or NiCl2/dcype as the catalyst, the reductive decyana-
tion of 1a under the optimal conditions gave 2a in 70% and
79% yield, respectively (eqn (6)). Based on these results, we are
confident that complex I was the true intermediate in the
catalytic cycle and acted as a key intermediate of the following
C–CN cleavage. Therefore, the proposed mechanism for this
Ni-catalyzed reductive decyanation reaction is shown in ESI.†
In summary, we have developed an efficient Ni-catalyzed reduc-
tive decyanation of nitriles which exhibited good functional-group
tolerance and afforded decyanated arenes in good to excellent
yields. In this protocol, the role of ethanol was assigned as the
reductant and the hydride source. Using ethanol endowed the
transformation with the advantages of being environmentally
friendly, less expensive and easy to handle. Further investigation
of the scope and potential applications of this methodology are
underway in our laboratories.
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This work was supported by the National Natural Science
Foundations of China (21773210, 21972125 and 21776260) and
the Fundamental Research Funds for the Provincial University
of Zhejiang (RF-B2019005).
´
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organic synthesis: background and detailed mechanisms, Elsevier,
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Conflicts of interest
21 T. Irrgang and R. Kempe, Chem. Rev., 2019, 119, 2524.
22 (a) L. Jin, J. Qian, N. Sun, B. Hu, Z. Shen and X. Hu, Chem. Commun.,
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There are no conflicts to declare.
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2276 | Chem. Commun., 2021, 57, 2273ꢀ2276
This journal is The Royal Society of Chemistry 2021