Cu2O-Catalyzed Conversion of Benzyl Alcohols Into Aromatic Nitriles via the Complete Cleavage of the C≡N Triple Bond in the Cyanide Anion

Article abstract of DOI:10.1002/asia.202100776

Nitrogen transfer from cyanide anion to an aldehyde is emerging as a promising method for the synthesis of aromatic nitriles. However, this method still suffers from a disadvantage that a use of stoichiometric Cu(II) or Cu(I) salts is required to enable the reaction. As we report herein, we overcame this drawback and developed a catalytic method for nitrogen transfer from cyanide anion to an alcohol via the complete cleavage of the C≡N triple bond using phen/Cu₂O as the catalyst. The present condition allowed a series of benzyl alcohols to be smoothly converted into aromatic nitriles in moderate to high yields. In addition, the present method could be extended to the conversion of cinnamic alcohol to 3-phenylacrylonitrile.

Full text of DOI:10.1002/asia.202100776

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Cu2O-Catalyzed Conversion of Benzyl Alcohols Into Aromatic
Nitriles via the Complete Cleavage of the C≡N Triple Bond in the
Cyanide Anion
Authors: Wenbo Liu, Peichen Tang, Yun-Lai Ren, Xinzhe Tian, Wankai
An, Xianfu Zheng, Yinggang Guo, and Zhenpeng Shen
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To be cited as: Chem. Asian J. 10.1002/asia.202100776
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10.1002/asia.202100776
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Cu2O-Catalyzed Conversion of Benzyl Alcohols Into Aromatic
Nitriles via the Complete Cleavage of the C≡N Triple Bond in the
Cyanide Anion
Wenbo Liu+,[a] Peichen Tang+,[b] Yi Zheng+,[a] Yun-Lai Ren,*[a] Xinzhe Tian,*[a] Wankai An,[a] Xianfu
Zheng,*[a] Yinggang Guo,[a] and Zhenpeng Shen[a]
Abstract: Nitrogen transfer from cyanide anion to the aldehydes is
emerging as a promising method for synthesis of aromatic nitriles.
However this method still suffers from a disadvantage that a use of
stoichiometric Cu(II) or Cu(I) salts is required to enable the reaction.
In the present article, we overcame this drawback, and developed a
catalytic method for the nitrogen transfer from cyanide anion to the
alcohols via the complete cleavage of the C≡N triple bond using
phen/Cu2O as the catalyst. The present condition allowed a series of
benzyl alcohols to be smoothly converted into aromatic nitriles in
moderate to high yields. In addition, the present method could be
extended to the conversion of cinnamic alcohol to 3-
phenylacrylonitrile.
Scheme 1. Methods for the synthesis of aromatic nitriles via the C≡N triple
bond cleavage of CN-.
Compared with the methods above, the formation of nitriles
via the nitrogen transfer of CN– is more challenging because the
C≡N triple bond is quite difficult to be broken.[12] Recently, this
challenge has been overcome by You, Lei and their co-workers
who have used a stoichiometric copper salt to enable conversion
of aldehydes to nitriles via the complete cleavage of the C≡N
triple bond in CN– (Scheme 1a).[13] Subsequently, Jin, Li and
their co-workers have described an analogous example where
aryl methyl ketones have been used as the substrates.[14]
However, the procedures above for the nitrogen transfer of CN–
require using a stoichiometric amount of Cu(II) or Cu(I) salts
because the used Cu(II) or Cu(I) salt is converted to CuO that is
inert as the promoter for the present reaction. By all
appearances, it should be desirable and challenging to develop
an effective catalyst to avoid the consumption of stoichiometric
Cu salts.[15] Aiming at this challenging, we have screened a large
number of Cu compounds and found that Phen/Cu2O is very
effective as the catalyst to enable the conversion of benzyl
alcohols into aromatic nitriles with K4[Fe(CN)6] as the nitrogen
source via the complete cleavage of the C≡N triple bond,
providing a promising method for synthesis of aromatic nitriles
from benzyl alcohols with less toxic and readily available
K4[Fe(CN)6] as the nitrogen source, and the results are herein
reported (Scheme 1b).
Introduction
Aromatic cyanation is an important kind of organic reactions
because the resulting products not only constitute the key
components of many agrochemicals, pharmaceuticals and
dyes,[1] but also can serve as versatile intermediates for various
synthetic targets such as aryl aldehydes, nitrogen-containing
heterocycles, amidines, tetrazoles amines, etc.[2] Among various
strategies for the aromatic cyanation,[3] transition-metal
catalyzed cyanation of aryl halides has been extensively
investigated.[4] Another kind of convenient methods is the
oxidative condensation between aryl aldehydes and ammonia or
its surrogate.[5] By comparison, it seems to be more fascinating
to use benzyl alcohols[6] as the substrate because the alcohols
are more inexpensive and easily available. For example, Wang,
Yang, Xiao and co-workers have used the Ru catalyst to enable
the amination-dehydrogenation of alcohols with ammonia as the
nitrogen source.[7] Recently, Singh and co-workers have
described photocatalytic conversion of the alcohols to aryl
nitriles via the nitrogen transfer of sodium azide.[8] In addition,
ammonium formate,[9] TMSN3 (trimethylsilyl azide)[10] and NH2OH
[11]
have been used as the nitrogen source to carry out the
Results and Discussion
amination-dehydrogenation of alcohols.
[a] W. B. Liu, Prof. Dr. Y.-L. Ren, Y. Zheng, X. Z. Tian, W. K. An, Prof. X. F.
Zheng, Y. G. Guo, Z. P. Shen
College of Science,
Henan Agricultural University
Zhengzhou 450002 (P.R. China)
E-mail: renyunlai@126.com; zzutxz@126.com; zxf001001@126.com
[b] Dr. P. C. Tang
School of Chemical Engineering
Dalian University of Technology
116024 Dalian (P.R. China)
Figure 1. Reaction of 2-methylbenzyl alcohol catalyzed by various catalysts
(reaction conditions: 0.5 mmol substrate, 0.3 mmol K4Fe(CN)6, 0.075 mmol
Cu compound or Cat. 1-4, 2 mL DMSO, 2 MPa O2, 40 h, 140 oC; the loading
of phen, bipy or PPh3 was 0.5 mmol in the case of the last five experiments in
this figure, while these ligands were not used in the other cases).
[+] These authors contributed equally.
Supporting information for this article is available on the WWW under
https://doi.org/
1
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Initial investigations were carried out with 2-methylbenzyl alcohol
as the model substrate to identify a suitable catalyst system. As
shown in Figure 1, when 15 mol% CuBr2 was used as the
catalyst, 2-methylbenzonitrile product was obtained in very low
yield, along with 12 % 2-methylbenzaldehyde by-product that is
from the oxidative dehydrogenation of the alcohol. The reaction
with CuBr gave a similar result, while hardly any targeted
product was obtained in the case of CuO. In addition, we tested
the ability of several N-heterocyclic carbine-Cu catalysts (Figure
2), but the targeted product was obtained in only 2-7% yields.
Fortunately, a combination of 1,10-phenanthroline (phen) and
Cu2O allowed 2-methylbenzonitrile to be obtained in a high yield
(88%). Changing the ligand from 1,10-phenanthroline to 2,2′-
bipyridine (bipy) or PPh3 led to a significantly decrease in the
yield of the targeted product. Of the screened Cu compounds,
Cu2O turned out to be the most effective one.
Subsequently, the effect of the oxygen pressure on the
reaction was investigated (Figure 4). Hardly any targeted
product was obtained in the absence of oxygen, which revealed
that oxygen played an important role in the reaction. The
reaction under 0.1 MPa oxygen gave the targeted product in 5%
yield. The yield of the targeted product increased continuously
with elevating the oxygen pressure from 0.1 to 2 MPa, while the
yield become slightly lower when the oxygen pressure increased
from 2 MPa, suggesting that 2 MPa was the optimum pressure.
It is worth noting that excessively high oxygen pressure would
lead to the formation of 2-methylbenzamide. For example, no 2-
methylbenzamide was observed in the case of 1.5 MPa oxygen,
whereas the reaction with 1.5 MPa oxygen gave 2-
methylbenzamide in 8% yield.
Figure 2. Several N-heterocyclic carbine-Cu catalysts.
After identifying an effective catalyst, we optimized other
reaction conditions. We performed the reactions using
K3Fe(CN)6 or KCN as the nitrogen source (Scheme 2), but the
obtained yields were lower than that in the case of K4Fe(CN)6
(Figure 1), indicating that K4Fe(CN)6 was the optimal one among
the screened nitrogen sources. As seen from Figure 3, the
reaction was highly dependent on the type of the solvent. The
use of toluene, tetrahydrofuran (THF), 1,4-dioxane and
acetonitrile as the solvents gave the targeted product in 13-22%
yields, while moderate yields were obtained in the case of N-
methyl-2-pyrrolidone (NMP) and N,N-dimethylformamide (DMF).
Of the screened solvents, dimethyl sulfoxide (DMSO) was the
most effective. It is noteworthy that the main by-product was 2-
methylbenzaldehyde in most cases, whereas the use of THF
was an exception where 48% 2-methylbenzoic acid by-product
Figure 4. Effect of O2 pressure on the reaction (reaction conditions: 0.5 mmol
2-methylbenzyl alcohol, 0.3 mmol K4Fe(CN)6, 0.075 mmol Cu2O, 0.5 mmol
phen, 2 mL DMSO, 2 MPa O2, 40 h, 140 oC).
A series of representative benzyl alcohols were tested to
explore the scope and generality of this reaction. As shown in
Table 1, various benzyl alcohols underwent the transformation to
give the targeted product in moderate to high yields, along with
benzamide or benzaldehyde by-products. The presence of
electron-donating groups bonded to the benzene ring decreased
the yields of the targeted products, but increased the conversion
of substrates. For example, 4-bromobenzyl alcohol was
converted to 4-bromobenzonitrile in 81% yield with 95%
conversion (Table 1, entry 1), while the same condition allowed
4-methoxybenzyl alcohol to be converted to the targeted product
in 49% yield with 100% conversion (Table 1, entry 2). It is worth
noting that the transformation of 4-methoxybenzyl alcohol gave
was observed. In addition,
a
small amount of 2-
methylbenzamide was produced in the case of DMSO.
by-products
such
as
4-methoxybenzaldehyde,
4-
methoxybenzoic acid and so on from oxidation of the alcohol in
as high as 51% total yield. These results indicate that the
presence of electron-donating groups is beneficial for
dehydrogenation of the alcohol to the aldehyde, but would
decrease the reactivity of the substrate in the step of conversion
of the aldehyde to the targeted product. So we had to increase
the reaction temperature to 140 oC in the case of the benzyl
alcohols with electron-donating groups (Table 1, entries 3-6). It is
worth noting that the presence of electron-withdrawing group
would increase the yield of benzamide by-products. For
instance, the reaction of the benzyl alcohols with alkoxy or
amino groups gave only 1-4% benzamide by-products, whereas
this kind of by-products were obtained in as high as 10-21%
yields in the case of using 4-fluorobenzyl alcohol, 4-chlorobenzyl
alcohol and 3,4-dichlorobenzyl alcohol as the substrates.
Interestingly, although 2-methylbenzyl alcohol had a bigger
steric hindrance around the reactive site than 4-methylbenzyl
alcohol, it was converted to the targeted product in higher yield
than the latter, due to the formation of larger amount of 4-
methylbenzamide by-product in the case of 4-methylbenzyl
alcohol (Table 1, entry 12 vs 13), which suggested that the steric
Scheme 2. Reaction of 2-methylbenzyl alcohol using different cyanide sources.
(reaction conditions: 0.5 mmol substrate, nitrogen source, 0.075 mmol Cu2O,
0.5 mmol phen, 2 mL DMSO, 2 MPa O2, 40 h, 140 oC).
Figure 3. Effect of the solvent on the reaction (reaction conditions: 0.5 mmol
2-methylbenzyl alcohol, 0.3 mmol K4Fe(CN)6, 0.075 mmol Cu2O, 0.5 mmol
phen, 2 mL solvent, 2 MPa O2, 40 h, 140 oC).
2
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hindrance would restrain the formation of the amide by-product.
1-naphthalenemethanol was a good substrate and gave the
nitrile product in 91% yield (Table 1, entry 16), but the reaction
of 9-anthracenemethanol gave the targeted product in only 52%
yield (Table 1, entry 17). The reaction of 4-pyridinemethanol also
proceeded well, but the obtained main product was 4-
pyridinecarboxamide (Table 1, entry 18). Interestingly, 2-
furanmethanol was converted to 2-furoic acid rather than the
nitrile product (Table 1, entry 19). In addition, the present
method was efficient for the conversion of cinnamic alcohol to 3-
phenylacrylonitrile, and the nitrile product was obtained in 81%
yield (Table 1, entry 20).
Subsequently, several control experiments were performed
to gain insight into the reaction mechanism. As shown in
Scheme 3a, 4-methoxybenzyl alcohol underwent the oxidative
dehydrogenation to give the aldehyde product in 77% yield in
the absence of K4[Fe(CN)6], and the reaction between the
aldehyde and K4[Fe(CN)6] went well under our condition. These
results indicate that the present transformation is a stepwise
reaction where oxidative dehydrogenation of the alcohol to the
aldehyde is followed by conversion of the aldehyde to the nitrile.
A small amount of 4-methoxybenzoic acid by-product was
observed under our conditions, hence it was possible that the
present reaction underwent the formation, decarboxylation and
cyanation of 4-methoxyphenylacetic acid, but this possibility was
ruled out based on the following result: The present condition did
not allow 4-methoxyphenylacetic acid to be converted to the
nitrile product (Scheme 3b).
Table 1. Conversion of various alcohols to aromatic nitriles.[a]
Entry
1[e]
Substrate
Product[b]
Yield (%)[c]
81
49[d]
86[d]
2[e]
3
Scheme 3. Control experiments for the investigation on the intermediates (for
68
4
the reaction conditions, see Scheme S1 in the supporting information).
62
80
5
6
85[d]
81[d]
7[f]
8[f]
9[e]
74
10[e]
11[g]
12[e]
86
Scheme 4. Control experiments for the mechanistic investigation (for the
72[d]
80[d]
reaction conditions, see Scheme S2 in the supporting information).
Afterwards, we wanted to clarify the roles of Cu2O, 1,10-
phenanthroline (phen) and K4[Fe(CN)6] in the step of the
oxidative dehydrogenation of the alcohol. The dehydrogenation
hardly occurred in the presence of O2/Cu2O (Scheme 4a), while
an addition of phen resulted in the formation of 75% 4-
methoxybenzaldehyde (Scheme 4b). These results suggest that
phen is indispensable in this step, which is possibly attributed to
that phen can effectively disperse the hardly soluble Cu2O to
form the catalytically active species by its coordination to Cu
species. In addition, the effect of phen as the ligand on the
electronic configuration of Cu species is one of the main
reasons. As shown in Scheme 4c, the dehydrogenation hardly
occurred in the absence of Cu2O, revealing that phen/Cu2O
played the role of the catalyst in the step of the conversion of the
alcohol to the aldehyde. Interestingly, when Cu2O was absent,
5% 4-methoxybenzonitrile product was formed (Scheme 4d),
which revealed that 4-methoxybenzaldehyde could directly react
with K4[Fe(CN)6].
88[d]
13
63
80
14
15
16[g]
17[g]
91
52
75
64
81
18
19[e]
20
[a]
Reaction conditions: 0.5 mmol 2-methylbenzyl alcohol, 0.3 mmol
K4Fe(CN)6, 0.075 mmol Cu2O, 0.5 mmol phen (1,10-phenanthroline), 2 mL
[c]
DMSO, 2 MPa O2, 40 h, 140 oC. [b] Determined by 1H-NMR and 13C-NMR.
Isolated yield. [d] The yield was determined by GC with an internal standard. [e]
120 oC. [f] 0.05 mmol Cu2O, 120 oC. [g] 0.1 mmol Cu2O, 120 oC.
3
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Scheme 5. C13-labelling experiments (for the reaction conditions, see Scheme
of transition metal salts to enable the nitrogen transfer from
cyanide anion to the aldehydes or the alcohols. Compared with
S3 in the supporting information).
previous methods for synthesis of aromatic nitriles from benzyl
[10]
alcohols with ammonia,[7] sodium azide[8] or TMSN3
as the
Next, we performed several control experiments to clarify
where the carbon atom of the cyano group in the nitrile product
came from. When either K4[Fe(13CN)6] or 13C-DMSO was used,
no 13C-labelled product was formed (Scheme 5), which revealed
that both K4[Fe(CN)6] and DMSO did not provide the carbon to
the nitrile product, thus it was reasonable that the carbon atom
of the cyano group was from the alcohol under our condition. In
addition, the nitrogen atom came obviously from K4[Fe(CN)6]
because no other compound apart from this reagent contained
the nitrogen atom in the reaction system. These results revealed
that K4[Fe(CN)6] underwent the complete cleavage of the C≡N
triple bond in the present reaction.
nitrogen source, the present method has an advantage of using
readily available and less toxic nitrogen source.
Experimental Section
1. General comments
All procedures for the cyanation were carried out in a 40
mL stainless steel autoclave lined with Teflon. N-heterocyclic
carbine-Cu catalysts were synthetized based on previous
literature.[16] All commercially available chemicals were used
directly as purchased without further purification unless
otherwise stated. GC-MS spectra was recorded on an Agilent
At last, we put forward a plausible mechanism with benzyl
alcohol as the representative substrate based on the
observation above and previous literatures.[13,14] As shown in
6890/5973N
gas
chromatography-mass
spectrometry
Scheme 6, the alcohol
I undergoes firstly the oxidative
instrument. H-NMR and 13C-NMR spectra were recorded on a
Bruker 400 MHz instrument. Gas chromatography analyses
were performed on a Varian CP-3800 instrument with a FID
detector and a CP-WAX 57CB FS capillary chromatographic
column.
1
dehydrogenation to give the aldehyde II under the catalysis of
1,10-phenanthroline/Cu2O, which be followed by the formation of
acyl radical III from Cu-catalyzed oxidation via the single
electron transfer. The acyl radical III reacts with FeII(CN-)6 to give
the FeII-bonded carbon-centered radical IV. Then the reaction
between the radical IV and the oxygen molecule gives benzoyl
isocyanate VI. Finally, a carbon dioxide molecule is eliminated
from the benzoyl isocyanate VI to give benzonitrile product. It is
worth noting that transition metals catalyzed conversion of
benzoyl isocyanate to benzonitrile has been reported in previous
literatures,[13,17] but the mechanism pathway for this step cannot
be clarified at the present stage.
2. General procedure for Cu2O-catalyzed conversion of
benzyl alcohols into aromatic nitriles
To a stainless steel autoclave lined with Teflon, 0.5 mmol
substrate, 0.3 mmol K4Fe(CN)6, 0.5 mmol 1,10-phenanthroline,
Cu2O (0.05, 0.075 or 0.1 mmol) and 2 mL DMSO were added.
Then the reactor was filled with 2 MPa oxygen, and was heated
under magnetic stirring at 120 or 140 °C for 40 h. Once the
reaction time was reached, the mixture was cooled to room
temperature, diluted with 5 mL ethyl acetate, filtered via a
Celite pad, and washed with 10 mL ethyl acetate. The organic
phase was washed with 6 mL water, dried with anhydrous
sodium sulfate and concentrated in vacuum. GC analysis
provided the GC yields of the products with an internal
standard. In addition, the crude product from another parallel
experiment was purified by column chromatography, and
identified by 1H-NMR and 13C-NMR.
Acknowledgements
The authors would like to thank the Key R & D and promotion
projects in Henan Province (Grant No. 212102310372), the
Natural Science Foundation of Henan Province (Grant No.
212300410358) and the financial supports from the National
Natural Science Foundation of China (Grant No. 21603060).
Scheme 6. Proposed pathway for the present reaction.
Conclusion
In conclusion, we found an effective catalyst for the
conversion of benzyl alcohols into aromatic nitriles with
K4[Fe(CN)6] as the nitrogen source via the complete cleavage of
the C≡N triple bond, which avoided the consumption of
stoichiometric Cu salts in previous reports.[13,14] A series of
alcohols including benzyl alcohols and cinnamic alcohol
underwent the present transformation to provide the targeted
products in moderate to high yields. The present method was
compatible with various groups, e.g. alkyl, alkoxy, fluoro, bromo,
chloro, methoxycarbonyl and N,N-dimethylamino group. To our
knowledge, this is the first example for using a catalytic amount
Keywords: Cuprous oxide • Aromatic nitriles• Benzyl alcohols •
Catalysis • Potassium ferrocyanide
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10.1002/asia.202100776
Chemistry - An Asian Journal
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A catalytic method was firstly developed for the nitrogen transfer from cyanide anion to the alcohols via the complete cleavage of the
C≡N triple bond using Phen/Cu2O as the catalyst. The present condition allowed various benzyl alcohols to be smoothly converted
into aromatic nitriles in moderate to high yields.
6
This article is protected by copyright. All rights reserved.