Nickel/Cobalt-Catalyzed Reductive Hydrocyanation of Alkynes with Formamide as the Cyano Source, Dehydrant, Reductant, and Solvent

Article abstract of DOI:10.1002/adsc.202000935

A Ni/Co co-catalyzed reductive hydrocyanation of various alkynes was developed for the production of saturated nitriles. Hydrocyanic acid is generated in situ from safe and readily available formamide. Formamide played multiple roles as a cyano source, dehydrant, and reductant for the Ni^II pre-catalyst and vinyl nitriles, along with acting as the co-solvent in this reaction. Detailed mechanistic investigation supported a pathway via hydrocyanation of C≡C bond and the subsequent reduction of C=C bond. Wide substrate scope, the employment of a cheap and stable nickel salt as pre-catalyst, a safe cyano source and convenient experimental operation render this hydrocyanation practical for the laboratory synthesis of saturated nitriles. (Figure presented.).

Full text of DOI:10.1002/adsc.202000935

Title: Ni/Co Catalyzed Reductive Hydrocyanation of Alkynes with
Formamide as the Cyano Source, Dehydrant, Reductant and
Solvent
Authors: Jin Zhang, Cui-Ping Luo, and Luo Yang
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.202000935
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10.1002/adsc.202000935
Advanced Synthesis & Catalysis
UPDATE
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Nickel/Cobalt-Catalyzed Reductive Hydrocyanation of Alkynes
with Formamide as the Cyano Source, Dehydrant, Reductant,
and Solvent
Jin Zhang,a,b Cui-Ping Luo a and Luo Yang a*
a
Key Laboratory for Green Organic Synthesis and Application of Hunan Province,
College of Chemistry, Xiangtan University, Hunan, 411105, P. R. of China
Fax: +86-731-58292251; Tel: +86-731-59292229; E-mail: yangluo@xtu.edu.cn;
College of Material and Chemical Engineering, Hunan City University, Hunan, 413000, P. R. of China
b
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract: A Ni/Co co-catalyzed reductive hydrocyanation of the subsequent reduction of C=C bond. Wide substrate
various alkynes was developed for the production of saturated scope, the employment of a cheap and stable nickel salt as
nitriles. Hydrocyanic acid is generated in situ from safe and pre-catalyst,
a
safe cyano source and convenient
readily available formamide. Formamide played multiple experimental operation render this hydrocyanation practical
roles as a cyano source, dehydrant, and reductant for the NiII for the laboratory synthesis of saturated nitriles.
pre-catalyst and vinyl nitriles, along with acting as the co-
solvent in this reaction. Detailed mechanistic investigation
supported a pathway via hydrocyanation of C≡C bond and
Keywords: hydrocyanation; cyano source; reduction;
alkynes; formamide
precedents, the hydrocyanation either requires highly
toxic and volatile HCN or surrogates thereof, such as
acetone cyanohydrin or metal cyanide, while the
subsequent reduction of the C=C bond requires the
addition of a reductant and noble metal catalyst.
Introduction
Nitriles are an important compound class, not only due
to their prevalence in a variety of natural products,
pharmaceuticals and agrochemicals,[1] but also due to
their synthetic versatility as powerful precursors for a
myriad of functionalities, such as amides, carboxylic
[2]
acids, amines, and ketones.
Therefore, numerous
methods have been developed for the generation of
nitriles. Among them, the hydrocyanation of alkynes
offers a straightforward approach for the preparation
of vinyl nitriles using HCN, acetone cyanohydrin, or
metal cyanide as the cyano source.[3,4] The generated
vinyl nitriles could be hydrogenated to provide
saturated nitriles (reductive hydrocyanation of
alkynes) via a one-pot[5] or stepwise[6] procedure.
Specifically, one-pot reductive hydrocyanation of
alkynes without the use of HCN has been
accomplished with the use of a stoichiometric amount
of [Co(CN)5]3− under a H2 atmosphere (Scheme 1a)[5a,
5b] or a sub-stoichiometric amount of [Ni(CN)4]2− (0.5
equiv) in the presence of excess KCN with NaBH4 or
Zn as reducing agents;[5c] meanwhile, stepwise
reductive hydrocyanation has been realized through
the classic Ni-catalyzed hydrocyanation of alkynes
with HCN and subsequent Pd or Rh-catalyzed
hydrogenation (Scheme 1b).[6a-6c] However, in these
Scheme 1 Reductive hydrocyanation of alkynes with
different cyano source.
1
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10.1002/adsc.202000935
Advanced Synthesis & Catalysis
To avoid the use of toxic metals or metalloid
choice of phosphorus ligand likewise significantly
influenced this reaction, thus Xantphos[11] with a rigid
butterfly structure and a large bite angle of 114o was
found to be the optimal match for the Ni(acac)2
catalyst (entries 8-10). The addition of a nitrogenous
cyanides, a “combined cyano” source strategy has
been established, whereby “CN” is generated in situ
from N,N-dimethylformamide (DMF) and ammonia,
to supply the carbon and nitrogen atoms, respectively,
assisted by a Cu or Pd catalyst under oxidative
conditions. This has been recognized as a successful
strategy for the cyanation of arenes bearing directing
groups, indoles, aromatic boronic acids, and aryl
iodides, as demonstrated by the pioneering work of
Chang et al.[7] Subsequently, similar cyanations that
employ other compounds as the carbon and nitrogen
source were separately reported by Cheng, Yu, Sakai
and Jiao.[8] However, multi-step transformations and
complex and harsh oxidative reaction conditions are
required to convert the carbon and nitrogen source
reagents to a “CN”, resulting in diminished yields and
limited substrate scope. This drawback of the
“combined cyano” source strategy has prompted us to
design and develop convenient cyanation reactions
with formamide as a green cyano source (Scheme 1c).
Thus, the cyanation of (hetero)aryl halides and
hydrocyanation of alkynes/alkenes have been
successively developed in our group.[9] Our
methodology is based on formamide dehydration to
produce “HCN” (coordinated to metals), while the
released water is consumed by the hydrolysis of
another formamide molecule to produce formate as a
byproduct. These results further inspired us to devise
a possible cascade reduction of vinyl cyanides
obtained from the hydrocyanation of alkynes, by
harnessing the formate byproduct as the reductant.[10]
Herein, we report a Ni/Co co-catalyzed reductive
hydrocyanation of alkynes with formamide as the
cyano source, dehydrant, reductant and solvent.
ligand
(phen
I:
3,4,7,8-tretramethyl-1,10-
phenanthroline) had a marginal influence on the
reaction, with the yields decreasing slightly in the
absence of phen I, or when it was replaced with 1,10-
phenanthroline or 2,2'-bipyridine (entries 11-13).
Compared with our previous study on the
hydrocyanation of alkynes,[9a] the introduction of a
nitrogen ligand, dosage of the cobalt catalyst, and
reaction temperature were important for ensuring the
in situ reduction of vinyl nitrile intermediates to the
corresponding saturated nitriles. It is worth noting that
this reductive hydrocyanation generally works well
with formamide as the solvent, however its high
polarity is unfavorable for the dissolution of non-polar
alkyne substrates, thus anisole was added as the co-
solvent to increase the compatibility of various alkyne
substrates.
Table 1. Optimization of reaction conditions [a]
Entry Change from the “standard conditions”
3a (%)
88
1
2
3
4
5
6
7
8
9
none
without Ni(acac)2
0
NiCl2 instead of Ni(acac)2
NiSO4·6H2O instead of Ni(acac)2
without Co(acac)2
35
65
18
Co(OAc)2 instead of Co(acac)2
iBu3Al instead of Co(acac)2
without Xantphos
80
43
Results and Discussion
15
Based on the above speculation and our recent
work,[9] 1,2-diphenylethyne (1a) was chosen as the
model substrate for exploring our reductive
hydrocyanation strategy. Detailed optimization was
performed by evaluating NiII pre-catalysts, phosphorus
ligands, cobalt salts, and nitrogen ligands, revealing
that the combination of 5 mol% Ni(acac)2 / 15 mol%
Xantphos / 15 mol% Co(acac)2 / 10 mol% 3,4,7,8-
tretramethyl-1,10-phenanthroline (phen I) was the
most effective, affording the targeted reductive
hydrocyanation product 3a in 88% isolated yield
(Table 1, entry 1). The control experiments indicated
that the NiII pre-catalyst was crucial for this
transformation (entry 2); besides Ni(acac)2, NiCl2, and
NiSO4·6H2O could also be utilized, albeit delivering
lower yields (entries 3 and 4). In sharp contrast,
Co(acac)2 played a supplementary role, and could be
dppp instead of Xantphos as the phosphine
56
ligand
10
BINAP instead of Xantphos as the phosphine
ligand
without phen I
42
11
12
68
70
phen II (1,10-phenanthroline) instead of
phen I as nitrogen ligand
bipy (2,2'-bipyridine) instead of phen I as
nitrogen ligand
13
68
[a] Conditions: 1,2-diphenylethyne (1a, 0.2 mmol), Ni(acac)2 (0.01 mmol,
5 mol%), Xantphos (0.03 mmol, 15 mol%), Co(acac)2 (0.03 mmol, 15
mol%), phen I (3,4,7,8-tretramethyl-1,10-phenanthroline, 0.02 mmol, 10
mol%), formamide (1.0 mL) and anisole (0.2 mL) were reacted at 155
°C (oil bath temperature) for 18 h under argon atmosphere. Isolated
Yields.
Under the optimized conditions, symmetrical 1,2-
diphenylethynes bearing various types of substituents
(1a-1q) all underwent the desired reductive
hydrocyanation to afford the corresponding nitriles
(3a-3q) in moderate to good yields (Table 2). Indeed,
substrates with alkyl (1a-1i), alkoxy (1j-1n), halo (1o,
i
replaced by Ni(OAc)2 or Bu3Al (entries 5-7). The
2
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10.1002/adsc.202000935
Advanced Synthesis & Catalysis
1p) and trifluoromethyl (1q) substituents were all
readily employed. Furthermore, naphthalen-1-yl (1r)
and n-butyl (1s) substituted ethynes were also viable
substrates for this Ni/Co co-catalyzed reductive
cyanation. Unexpectedly, for unsymmetrical internal
alkynes, such as 1-phenyl-2-methylacetylene (1t), 2-
methyl-3-phenylpropanenitrile (3t) was detected
exclusively by GC-MS and isolated in 85% yield,
despite the possibility of the cyano group being
installed onto C1 or C2 of the unsymmetrical alkyne
to provide two regioisomers.
and branched regioisomers were predominantly
obtained over the linear isomers, possibly due to the
formation of a more stable benzyl nickel intermediate
during the hydrocyanation step. In sharp contrast, the
trifluoromethyl-substituted alkyne 4i afforded a single
linear product 6i, because the electron-withdrawing
trifluoromethyl group markedly increases the
electrophilicity of the terminal carbon.
Table 3. Scope of the mono-substituted acetylenes for this
reductive hydrocyanation [a]
Table 2. Scope of the 1,2-disubstituted ethynes for this
reductive hydrocyanation [a]
[a]
Conditions: alkyne (4, 0.2 mmol), Ni(acac)2 (0.01 mmol, 5 mol%),
Xantphos (0.03 mmol, 15 mol%), Co(acac)2 (0.03 mmol, 15 mol%),
phen I (3,4,7,8-tretramethyl- 1,10-phenanthroline, 0.02 mmol, 10
mol%) and formamide (1.0 mL) were reacted at 150 °C (oil bath
temperature) for 24 h under argon atmosphere. Isolated Yields. The
ratio for the two regio-isomers were determined by GC.
To elucidate the reaction mechanism of this
reductive hydrocyanation with formamide as the
cyano source, several control experiments were
performed. First, two possible intermediates, 2,3-
diphenylacrylonitrile (8a, Z and E mixtures) and 2,3-
diphenylacrylamide (7a, Z and E mixtures) were
prepared by the condensation of benzaldehyde with 2-
phenylacetonitrile and subsequent hydrolysis (Scheme
2a). Second, these two potential intermediates were
separately subjected to the optimized reaction
conditions to demonstrate that 2,3-diphenylacrylamide
(7a) could not be dehydrated and converted to the
desired vinyl product (Scheme 2b), and 2,3-
diphenylacrylonitrile (8a, Z and E mixtures) was
indeed reduced to provide reductive cyanation product
3a (Scheme 2c). These results not only ruled out the
possibility of a pathway involving the hydroamidation
of alkyne 1a and subsequent dehydration of amide 7a,
but also supported that nitrile 8a was the intermediate
for this reductive hydrocyanation. Third, the exact role
of the two transition metals (Ni and Co) was studied.
Using 2,3-diphenylacrylonitrile (8a) as the starting
material, a control experiment in the absence of
Ni(acac)2 (at the same time, formamide was replaced
by DMF, as no cyano source was needed for the
[a] Conditions: alkyne (
mol%), Xantphos (0.03 mmol, 15 mol%), Co(acac)2 (0.03
mmol, 15 mol%), phen (3,4,7,8-tretramethyl- 1,10-
phenanthroline, 0.02 mmol, 10 mol%), formamide (1.0 mL) and
anisole (0.2 mL) were reacted at 155 °C (oil bath temperature)
for 18 h under argon atmosphere. Isolated Yields.
1, 0.2 mmol), Ni(acac)2 (0.01 mmol, 5
I
Encouraged by the above results on the reductive
hydrocyanation of symmetrical 1,2-diarylethynes,
various terminal aromatic alkynes were then evaluated
as substrates for this reaction (Table 3, 4a-1i).
Similarly, various terminal aromatic alkyne
derivatives bearing electron-donating or electron-
withdrawing substituents on the phenyl moiety
underwent this reductive hydrocyanation smoothly to
afford saturated nitriles (5 and 6) in good yields.
Generally, the reaction followed Markovnikov’s rule
3
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10.1002/adsc.202000935
Advanced Synthesis & Catalysis
reduction step) provided saturated nitrile 3a in 78%
yield (Scheme 2d). In contrast, a similar reaction in the
absence of Co(acac)2 led to a very low yield (Scheme
2e), which strongly supported that the reduction of the
C=C bond was chiefly catalyzed by Co(acac)2. In light
of the results obtained from reaction optimization
(Table 1, entries 2 and 8), which indicated that the
Ni(acac)2/Xantphos combination was crucial for the
hydrocyanation of alkynes, the Ni and Co salts were
determined as being responsible for the
hydrocyanation of C≡C bonds and reduction of C=C
bonds, respectively. Then, a linear oct-1-yne (4j) was
further tested as a potential substrate for this reaction
to analyze the regioselectivity, which predominately
afforded linear saturated nitrile 6j (Scheme 2f). As the
cis-addition of the Ni-H bond to the C≡C bond to
produce the vinyl nickel intermediate (III-6j or III-5j)
is a crucial step for the hydrocyanation of alkynes, the
increased stability of intermediate III-6j due to its
lower steric hindrance between the hydrogen and
phosphorus ligand (compared with intermediate III-
5j) likely contributes to the linear selectivity. Finally,
the reaction progress regarding the generation of
product 3a, intermediate 8a, and the recovery of 1a
with reaction time was investigated to further support
the pathway by which alkynes were directly
transformed into acrylonitrile (8a), and then reduced
to provide saturated nitrile 3a (Figure 1). As can be
seen in Figure 1, byproduct 9a generated from the
direction reduction of alkyne 1a, accumulated during
this reaction, but it was an inactive intermediate in this
reductive hydrocyanation, thus excluding the
reduction-hydrocyanation pathway.
Scheme 2 Mechanistic experiments.
Figure 1 Reaction progress versus reaction time for the reductive hydrocyanation. The values for each measurement were
detected by GC (with an internal standard) from independent experiments under the optimized conditions but stopped after
the indicated reaction time.
4
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10.1002/adsc.202000935
Advanced Synthesis & Catalysis
Based on these results and literature reports using bond. A wide substrate scope, the use of a cheap and
metal cyanides as the cyano source,[4] a tentative stable nickel salt as a pre-catalyst, a safe cyano source,
mechanism for the reductive hydrocyanation of and convenient experimental operation are important
alkenes is proposed, as depicted in Scheme 3, with the advantages of this hydrocyanation protocol for the
reaction of 1,2-diphenylethyne (1a) as an example. The laboratory synthesis of saturated nitriles.
first step involves the Ni/Co co-catalyzed dehydration
of formamide to form hydrocyanic acid[9a] and
Experimental Section
hydrolysis of formamide molecules to produce
ammonium formate,[10] thus reducing NiIILn to provide
Ni0Ln (L = ligand). Then, oxidative addition of
hydrocyanic acid to Ni0Ln generates NiII intermediate
I, followed by coordination of alkyne 1a and the cis-
addition of the Ni-H bond to the C≡C bond to produce
intermediate III, which undergoes reductive
elimination to provide the hydrocyanation product 8a
in the E configuration and regenerates the Ni0Ln
catalyst. Vinyl nitrile 8a in the E configuration is
possibly partially converted to its Z configuration
assisted by Ni or Co at elevated reaction temperatures,
and both stereoisomers are reduced by the
Co(acac)2/ammonium formate combination to afford
saturated nitrile 3a.
2,3-Diphenylpropanenitrile (3a) by Reductive
Hydrocyanation of an Alkyne; Typical Procedure:
An oven-dried reaction vessel was charged with 1,2-
diphenylethyne (1a, 0.2 mmol, 35.6mg), Ni(acac)2 (5
mol%, 2.6 mg), Co(acac)2 (15 mol%, 7.7 mg),
Xantphos (15 mol%, 17.4 mg), 3,4,7,8-tetramethyl-
1,10-phenanthroline (phen I, 10 mol%, 4.7 mg),
formamide (1.0 mL) and anisole(0.2 mL) under argon
atmosphere. The vessel was sealed, heated and stirred
at 155 °C (oil bath temperature) for 18 h. Then the
resulting mixture was cooled to room temperature,
added with 10 mL brine and extracted with ethyl
acetate (3 × 10 mL). The organic layer was combined,
washed with brine (2 × 10 mL), dried with anhydrous
sodium sulfate and filtered. The filtrate was condensed
in vacuum to remove solvent and further purified by
column chromatography on silica gel with a mixture of
EtOAc/petroleum ether as eluent to give the product
(3a, 36.4 mg) in 88% yield.
Acknowledgements
This work was supported by the National
Natural Science Foundation of China (21772168)
and Effective Resource Utilization, the project of
innovation team of the ministry of education
(IRT_17R90).
Scheme 3. Proposed mechanism for the reductive
hydrocyanation.
The authors declare no competing financial
interest.
Conclusion
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Advanced Synthesis & Catalysis
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10.1002/adsc.202000935
Advanced Synthesis & Catalysis
UPDATE
Ni/Co Catalyzed Reductive Hydrocyanation of
Alkynes with Formamide as the Cyano Source,
Dehydrant, Reductant and Solvent
Adv. Synth. Catal. Year, Volume, Page – Page
Jin Zhang, Cui-Ping Luo and Luo Yang*
7
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