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Although the detailed mechanism is still under investigation,
we suggest the following catalytic cycle based on the above
observations and related literature (Scheme 4).5,14 First, the
oxidative addition of hydrogen cyanide to Ni(0) would result in
the formation of the H-Ni(II)-CN species, which would insert
onto the alkyne via syn-addition to afford an (E)-alkenyl nickel
complex A. The steric repulsion of the alkenyl with the nitrile
group possibly influences the regioselectivity of this step.5
Then, the alkenyl nickel complex would give the single
DOI: 10.1039/D0CC02938F
Pharm. Bull., 2019, 67, 397−403; (c) J. Long, J. Gao and
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T. V. Rajanbabu, Comprehensive Organic Synthesis II,
Hydrocyanation in Organic Synthesis, P1772−1793,
2014.
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hydrocyanation product
6
via reductive elimination.
Afterwards, second hydrocyanation would occur to afford the
π-allyl-Ni complex B. Finally, a second reductive elimination of
the more stable π-allyl-Ni complex C would lead to the desired
product of dihydrocyanation 3a and to regeneration of the
Ni(0) species.
7
8
In conclusion, we have developed a highly regio- and
stereoselective dihydrocyanation of 1,3-enynes using TMSCN
as cyanide source and MeOH as hydrogen source. Through this
approach, a wide range of pentenedinitrile products were
efficiently prepared with high levels of regio- and
stereoselectivity. The dinitrile products were conveniently
converted to poly-substituted pyridines. We believe that this
finding provides new insight into metal-catalyzed
hydrocyanation of internal alkynes. Our approach is also useful
for the synthesis of biologically important compounds. Further
investigations to elucidate the mechanistic intricacies of this
process, to apply this strategy to other reactions and to try to
reduce the catalyst loading are currently underway in our
laboratory.
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11 The configuration was confirmed by NOE analysis.
12 The spectral data is consistent with the literature: M.
Ye, G. Gao, A. J. F. Edmunds, P. A. Worthington, J. A.
Morris and J. Yu, J. Am. Chem. Soc., 2011, 133,
19090−19093.
This work was financially supported by the Recruitment
Program of Global Experts, the startup funding from Shanghai
Jiao Tong University. We thank Dr. Bastien Cacherat (SIOC,
Shanghai) for critical proofreading of this manuscript.
13 A. Kowalkowska, D. Suchołbiak, A. Jończyk. Eur. J. Org.
Chem., 2005, 925–933.
14 The insertion of H-Ni-CN to alkynes proceeds
predominantly in a syn-addition manner, see the
reference 2b.
Conflicts of interest
There are no conflicts to declare.
Notes and references
1
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