Selective aerobic oxidation of benzylic amines to aryl nitriles catalyzed by CuBr2/N-methyl imidazole

Article abstract of DOI:10.1016/j.tet.2018.06.054

A convenient and efficient copper-catalyzed aerobic oxidation of primary amines to aryl nitriles was described. Various benzylic and allylic amines were selectively oxidized to the corresponding nitriles in high yields using CuBr₂/NMI as the catalyst and O₂ as the oxidant. The oxidation reaction profiles monitored by ¹H NMR disclosed the scenario of the reaction path as well as the role of the additives. The addition of NMI increased the rate of reaction and suppressed the hydrolysis and the deamination.

Full text of DOI:10.1016/j.tet.2018.06.054

Accepted Manuscript
Selective aerobic oxidation of benzylic amines to aryl nitriles catalyzed by CuBr /N-
2
methyl imidazole
Yifan Shen, Yu Zhou, Lili Jiang, Guangni Ding, Luo Luo, Zhaoguo Zhang, Xiaomin Xie
PII:
S0040-4020(18)30754-3
10.1016/j.tet.2018.06.054
TET 29650
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 11 May 2018
Revised Date: 19 June 2018
Accepted Date: 20 June 2018
Please cite this article as: Shen Y, Zhou Y, Jiang L, Ding G, Luo L, Zhang Z, Xie X, Selective aerobic
oxidation of benzylic amines to aryl nitriles catalyzed by CuBr /N-methyl imidazole, Tetrahedron (2018),
2
doi: 10.1016/j.tet.2018.06.054.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Selective aerobic oxidation of benzylic
amines to aryl nitriles catalyzed by CuBr2/N-
methyl imidazole
Leave this area blank for abstract info.
Yifan Shen a,b, Yu Zhou a, Lili Jiang a, Guangni Ding a, Luo Luo a, Zhaoguo Zhang a, and Xiaomin Xie a,
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road,
Shanghai 200240, China

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Selective aerobic oxidation of benzylic amines to aryl nitriles catalyzed by
CuBr2/N-methyl imidazole
Yifan Shen a,b, Yu Zhou a, Lili Jiang a, Guangni Ding a, Luo Luo a, Zhaoguo Zhang a, and Xiaomin Xie a,
a School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China
b Zhiyuan College, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A convenient and efficient copper-catalyzed aerobic oxidation of primary amines to aryl nitriles
was described. Various benzylic and allylic amines were selectively oxidized to the
corresponding nitriles in high yields using CuBr2/NMI as the catalyst and O2 as the oxidant. The
oxidation reaction profiles monitored by 1H NMR disclosed the scenario of the reaction path as
well as the role of the additives. The addition of NMI increased the rate of reaction and
suppressed the hydrolysis and the deamination.
Available online
Keywords:
2009 Elsevier Ltd. All rights reserved
.
Aerobic oxidation
Copper catalyst
Benzylic amines
Aryl nitriles
N-methyl imidazole
———
Corresponding author. Tel.: +86-021-5474-8915; fax: +86-021-5474-8915; e-mail:xiaominxie@sjtu.edu.cn

2
Tetrahedron
ACCEPTED MANUSCRIPT
1. Introduction
Scheme 1. The oxidation of primary amines to nitriles
The oxidation of amines provides great opportunities for
2. Results and Discussion
nitrogen-containing building-blocks for the modern chemical
industry.1 Among them, aryl nitriles are valuable and useful
building blocks for the manufacture of pharmaceuticals,
agrochemicals and polymers.2 The selective oxidation of amines
to nitriles could offer an alternative route3 which avoids using
dangerous and poisonous reagents, such as HCN and MCN
(M=Na, K).4 Although the oxidation of amines using
stoichiometric metal or organic oxidants has been reported, 5 the
aerobic oxidation is more attractive considering that oxygen is an
abundant, low-costing, and environmentally benign oxidant.6
4-Methoxybenzylamine (1a) was chosen as the model
substrate to explore the reactivity of the copper catalyzed
oxidation of amines. Because CuCl/O2/pyridine was a classical
catalytic
system
for
the
oxidation
of
phenols,
diphenylmethanimine and catechols etc.7, we first tested the
oxidation of 1a in toluene with CuCl (10 mol%) as the catalyst
and pyridine (30 mol%) as the additive. After the reaction
mixture was refluxed for 24 h under oxygen atmosphere, 4-
methoxybenzylamine (1a) was converted completely, 64% of
benzonitrile (2a) was obtained, together with benzaldehyde (4a)
and 12% of imine 5a (Table 1, entry 1). Then we screened copper
salts to improve the selectivity for nitrile. The yield of nitrile 2a
increased notably when CuBr was used as the catalyst (Table 1,
entry 2); while imine 5a was formed as the major product in the
presence of CuI (Table 1, entry 3). The oxidation state of copper
compounds also influenced the selectivity of the oxidation. CuBr2
showed better selectivity than CuBr for the formation of nitrile
(Table 1, entry 4). When Cu (0) was used with catalytic amount
of pyridine and ammonium bromide, the catalytic system
produced imine 5a as the major product (Table 1, entry 5).
Neither copper acetate nor copper nitrate gave better yield than
copper bromide did. Therefore, the coordinating ability of anion
in the copper salt also played an important role in the oxidation.
Then the influence of solvents on the aerobic oxidation of amines
with CuBr2 as the catalyst was surveyed. The selectivity of the
oxidation in 1,4-dioxane decreased greatly. When DMF was used
as the solvent, the yield of imine 5a decreased to 3%, but the
yield of benzaldehyde (4a) increased and the reactivity of the
catalytic system also decreased (Table 1, entry 10). The yield of
2a increased to 88% when the oxidation occurred in DMSO
(Table 1, entry 11). The oxidation in CH3CN gave imine 5a as
the major product. So, DMSO was chosen as the solvent for
further screening.
Copper complexes are cheap, versatile and powerful catalysts
for many aerobic oxidations which were found in the active site
of enzymatic oxidizing systems, and used in industrial processes
(for example, Glaser − Hay alkyne coupling and phenol
polymerization).7 Recently, Cu complex/co-catalyst systems had
been devised for the aerobic oxidation of primary amines to the
corresponding imines or nitriles.8 Stahl's group reported the
effective aerobic oxidation of primary amines to the nitriles
catalyzed by (4,4'-tBu2bpy)CuI/ABNO (ABNO
=
9-
azabicyclo[3.3.1]nonan-3-one-N-oxyl).8a However, the aerobic
oxidation of primary amines to nitriles catalyzed with copper
complexes as the single catalyst was elusive. Kametani and co-
workers reported the first aerobic oxidation of amines to nitriles
with poor yields which used one equivalent copper(I) chloride in
pyridine under an oxygen atmosphere. 9 The oxidation of primary
amines (1, Scheme 1) to nitriles (2) is involved in the sequential
oxidation of amine (1) and the intermediate (imines, 3). However
further reaction of the imines (3) is likely to be complicated by
the competing hydrolysis to form the aldehyde (4) and
nucleophilic attack by amines (1) followed by deamination to
give symmetrical imines (5) 10. To improve the catalytic activity
and avoid the formation of aldehydes (4) or imines (5) as the
byproducts, stoichiometric copper salts or/and molecular sieves
were usually used.11 Azaaromatic compounds, such as pyridines
and isoquinoline, were also used as stoichiometric amounts of
additive,12 but few studies were there on the role of these
compounds. We envision that catalytic amount of azaaromatics
may adjust the catalytic activity and selectivity of copper
catalysts for the oxidation of amines, because alkyl amines and
heterocycles have been used as ligands to increase the reactivity
and stability of dinuclear LnCu2 – O2 active center for the
phenolate oxidation and influence the selectivity between ortho-
oxygenation and oxidative coupling of phenols.13 Herein, we
report our exploring on the effect of catalytic amount
azaaromatics on the selectivity of the copper catalyzed aerobic
oxidation of primary amines, and develop a convenient and
effective copper catalytic system, CuBr2/NMI (N-methyl
imidazole), for the aerobic oxidation of benzylic primary amines
to nitriles.
Table 1. The effect of catalysts and solvents on the oxidation
of 4-methoxybenzylamine a
Yield (%)b
Entry
[Cu]
Solvent
Conv. (%) b
2a 4a 5a
64 12 12
1
2
3
4
5
CuCl
CuBr
Toluene
Toluene
Toluene
Toluene
Toluene
100
100
93
74
27
80
29
6
5
5
7
10
31
8
CuI
CuBr2
100
100
Cu(0) c
Cu(OAc) 2
·H2O
32
6
7
8
Toluene
Toluene
Toluene
100
100
100
55
6
22
Cu(NO3) 2
·3H2O
Cu(OTf) 2
·xH2O
CuBr2
54 15 16
31 10 29
40 17 21
9
1,4-dioxane
DMF
100
87
10
11
CuBr2
52 29
88
3
2
CuBr2
DMSO
100
7

3
12
CuBr2
CH3CN
89
10
4
37
2,2'-Dipyridine
ACCEPTED MANUSCRIPT
7
100
21 59 10
73 17
a
(15 mol%)
Reaction conditions: 4-Methoxybenzylamine (1a, 1.0 mmol), copper
compound (10 mol%), pyridine (30 mol%), solvent (2 mL), 100oC, 24 h;
oxygen was provided by a balloon.
8
Et3N (30 mol%)
DBU (30 mol%)
tBuOK (30 mol%)
K2CO3 (30 mol%)
K3PO4 (30 mol%)
NMI (30 mol%)
NMI (30 mol%)
NMI (30 mol%)
NMI (20 mol%)
NMI (30 mol%)
NMI (30 mol%)
90
100
100
100
100
100
100
100
100
100
0
-
9
37 34 18
34 20 23
b
1
10
11
12
13c
14d
15e
16
17f
18g
Conversion and yields were determined by H NMR analysis (internal
standard: 4,4’-di-tert-butyl-1,1’-bipheny.
-
7
16 42
c 0.3 Equivalent of ammonium bromide was added.
8
-
43
16
-
68
Next, the influence of additives on the copper catalyzed
aerobic oxidation of the primary amine was investigated. In the
presence of 30 mol% pyridine, the oxidation of amine gave
benzonitrile (2a) in 88% yield (Table 2, entry 1), while, omission
of the additive led to drastic decrease of the selectivity for nitrile
(Table 2, entry 2). When pyridine was replaced with DMAP (4-
dimethylaminopyridine) or NMI (N-methyl imidazole) in the
oxidation, the yield of 2a was further improved, and the imine
was not observed. The oxidation with NMI as the additive
generated 2a in 96% yield (Table 2, entry 4). However, imidazole
and 2-methyl imidazole were inferior additives (Table 2, entries 5
and 6).14 Benzaldehyde (4a) was the major product in the case of
2,2'-Bipyridine as the additive (Table 2, entry 7). When the
aliphatic amine was used as additive, the yield of the aldehyde as
byproduct increased (Table 2, entry 8). Inorganic base did not
favor the formation of the nitrile at all (Table 2, entries 11-12).
These results showed that catalytic amount of additive containing
nitrogen plays an important role in the oxidation. Lowering the
reaction temperature favored the formation of imine, and no
aldehyde was observed (Table 2, entry 13). When the
temperature was increased to 120oC, the yield of aldehyde was
increased (Table 2, entry 14). Decreasing the loading of CuBr2 or
NMI resulted in slightly decreased yield of nitrile (Table 2,
entries 15 and 16). The oxidation under air remained good
conversion, but the yield of aldehyde increased greatly (Table 2,
entry 17). Therefore, the optimized reaction conditions for the
copper catalyzed aerobic oxidation of benzyl amine 1a to the
nitrile 2a were identified as following: CuBr2 (10 mol%) as the
catalyst, NMI (30 mol%) as the additive, DMSO as the solvent,
under oxygen provided by a balloon, at 100 oC.
87 22
92
94
5
6
1
0
51 49
-
-
-
-
a
4-Methoxybenzylamine (1a, 1.0 mmol), CuBr2 (10 mol%), Additive (30
mol%), DMSO (2 mL), 100oC, 24 h; oxygen was provided by a balloon.
b
1
Conversion and yields were determined by H NMR analysis (internal
standard: 4,4’-di-tert-butyl-1,1’-biphenyl).
c Reaction temperature: 80 oC.
d Reaction temperature: 120 oC.
e 5 mol% of CuBr2 was used.
f Reaction occurred under air.
g Without CuBr2.
Table 3. The aerobic oxidation of primary amines catalyzed
by CuBr2/NMI
Table 2. The effect of the additives, temperature and loading
of catalyst on the selective aerobic oxidation of amines a
Yield (%)b
Entry
Additive
Conv. (%)b
2a 4a 5a
88
41 20 19
Pyridine
(30 mol%)
-
1
2
3
100
100
100
7
2
a
Amine (1, 3.0 mmol), CuBr2 (10 mol%), NMI (30 mol%), DMSO (6
mL), 100oC, 24 h; oxygen was provided by a balloon, isolated yield.
b The oxidation was conducted on a 10 mmol scale.
c The staring amine was in Z:E= 1:1 ratio
DMAP
92
96
8
4
-
-
(30 mol%)
NMI
4
5
100
100
(30 mol%)
Imidazole
(30 mol%)
2-Methyl
Imidazole
(30 mol%)
The scope of the copper catalyzed aerobic oxidation of
primary amines was then explored under the optimized
conditions. As shown in Table 3, the aerobic oxidation of benzyl
primary amines and allyl primary amines afforded efficiently a
number of nitriles (2). Both 4-tert-butylbenzylamine (1b) and
electron-neutral [1,1'-biphenyl]-4-ylmethanamine (1c) were
51 17 13
6
100
32
-
34

4
Tetrahedron
oxidized selectively to the nitriles in excellent yields. The
aerobic oxidation of primary amines to nitriles always generated
ACCEPTED MANUSCRIPT
reactivity decreased slightly in the oxidation of benzyl amines
with electron-withdrawing group on the aromatic rings. The
oxidation of 4-(trifluoromethyl) benzyl amine (1h) afforded
nitrile 2h in 76% yield. High activity and selectivity were
obtained in the reactions of bulkier benzyl amines. 1-
Naphthonitrile (2j) and 2,6-dimethylbenzonitrile (2l) were
obtained in 89% yield. Furthermore, the aerobic oxidation system
tolerates hetero aromatic and halogen atoms. The oxidation of
pyridin-3-ylmethanamine (1i) proceeded smoothly to generate
the corresponding nitrile (2i) in 92% yield. 4-Bromobenzyl
amine (1g) was oxidized to give 4-bromobenzonitrile (2g) in
89% yield, and no coupling product was observed. 1,4-
Phenylenedimethanamine (1m) was also oxidized efficiently to
terephthalonitrile (2m) in 90% yield. The aerobic oxidation of
allyl amines (1n and 1o) afforded the corresponding nitriles in
moderate yield. In addition, the scaled-up aerobic oxidation ran
effectively. The oxidation of (1a) and (1i) at 10 mmol scale
generated 4-methoxybenzonitrile (2a) in 90% yield and
nicotinonitrile (2i) in 80% yield, respectively. Regretfully, this
catalytic system did not work efficiently for the aerobic oxidation
of aliphatic primary amines to nitriles. The oxidation of 3-
phenylpropylamine gave the imine in 22% yield and the aldehyde
in 27% yield.
the aldehyde 4a and the imine 5a as byproducts.
Scheme 2. The oxidation of imine 5a in the catalytic system
Figure 1. Reaction profile of CuBr2 catalyzed aerobic oxidation
of 1a in DMSO under oxygen (A: without NMI; B: with NMI)
Scheme 3. Proposed mechanism of the aerobic oxidation of
primary amine to nitriles catalyzed by CuBr2
Based on our optimization for the aerobic oxidation of amines
to nitriles, the addition of catalytic amount NMI improved the
selectivity of the oxidation. The reaction profiles were also
shown in Figure 1 (B). The additive increased the oxidation rate
of 1a and phenylmethanimine (3a), and the intermediate 3a' was
converted efficiently to nitrile 2a by suppressing the hydrolysis
of 3a and the deamination from 3a’. So the additive may work as
ligands to increase the rate of oxidation and suppress the
deamination and the hydrolysis.
A
B
To investigate the reaction pathway of this selective oxidation
and the effect of the additive, the reaction profiles were
monitored by H NMR spectroscopy (Figure 1, A and B). In the
3. Conclusions
1
In summary, we have developed a convenient and efficient
copper catalyzed aerobic oxidation of primary amines to nitriles.
Various benzyl and allyl amines were effectively oxidized to the
corresponding nitriles in high yields with CuBr2/NMI system.
The reaction profiles monitored by 1H NMR spectroscopy
disclosed the scenario of the aerobic process as well as the effect
of the additive. NMI may work as the ligand and nucleophile to
increase the oxidation rate and help the key intermediate (aminal)
convert effectively to the nitrile by suppressing the hydrolysis
and the deamination.
aerobic oxidation of 4-methoxybenzylamine (1a) catalyzed by
CuBr2 (10 mol%) in DMSO (Figure 1, A), the benzyl amine 1a
was quickly converted to the intermediate 3a' whose structure
was similar to the imine 5a based on 1H NMR spectra (Figure S1
in Supporting Information), and the concentration of the
intermediate 3a' began to decrease when 1a was fully converted.
The nitrile 2a was formed gradually after 25 mins. The aldehyde
4a was not observed until the concentration of amine 1a was
quite low. We speculated that 3a' was aminal, because the
concentration of 2a and 4a increased with the decay of 3a',
moreover, the imine 5a did not converted in the catalyst system
(Scheme 2). The catalyst appeared to deactivate after 20 h. Based
on these observations, we proposed a pathway of this aerobic
oxidation without additives as shown in Scheme 3. The primary
amine 1a was first oxidized to phenylmethanimine (3a) catalyzed
by the copper (II) complex, then 3a was quickly attacked by the
amine 1a to form N-benzyl-1-phenylmethanediamine (3a'). With
decreasing concentration of 1a, the reverse reaction was
favorable, and N-benzyl-1-phenylmethanediamine (3a’) started to
decompose to give 1a and phenylmethanimine (3a) for the
oxidation. When the concentration of 1a was quite low, the
competing hydrolysis of phenylmethanimine (3a) occurred to
form the aldehyde 4a as a byproduct. In addition, amine 1a may
also work as a ligand to stabilize the copper catalyst. So
deamination from the intermediate 3a’would take place to give
the imine 5a as the concentration of 1a was low. Therefore, the
4. Experimental section
4.1. General information
Commercially available reagents were used throughout
without further purification other than those detailed below. All
oxidation reactions were carried out under an atmosphere of
1
oxygen provided by a balloon. HNMR spectra were recorded at
400 MHz with TMS as internal standard. 13C NMR spectra were
recorded at 100 MHz and referenced to the central peak of 77.0
ppm for CDCl3. Coupling constants (J) are reported in Hz and
refer to apparent peak multiplications. Flash column
chromatography was performed on silica gel (300- 400 mesh).
4.2. Typical procedure for CuBr2/NMI catalyzed aerobic
oxidation of primary Amines

5
To a 100 mL eggplant type Schlenk flask were added CuBr2
(67.0 mg, 0.3 mmol), corresponding amine (3 mmol) and a
solution of NMI (73.8 mg, 0.9 mmol) in DMSO (6 ml). The flask
was evacuated and purged with oxygen for three times before the
flask was attached to a balloon filled with oxygen. Then the flask
was heated at 100 °C for 24 hours. After the flask was cooled
down and the reaction mixture turned into green color, water (15
mL) and dichloromethane (15 mL) was added into the mixture.
The water layer was extracted with dichloromethane (5 mL×3)
and the organic layers were combined. After removing the
solvent, residue was purified by column chromatography
(PE/EA=100:1) to give the product.
o-Tolunitrile (2k).16 Yield: 88% (colorless liquid, 309.3
1
ACCEPTED MANUSCRIPT
mg); H NMR (400 MHz, CDCl3): δ 7.56 (d, J = 7.7 Hz, 1H),
7.47 (td, J = 7.7, 1.1 Hz, 1H), 7.34 – 7.21 (m, 1H), 2.52 (s, 3H);
13C {1H} NMR (100 MHz, CDCl3):δ 141.5, 132.4, 132.1, 129.9,
125.9, 117.8, 112.3,20.1.
2,6-Dimethylbenzonitrile (2l).21 Yield: 89% (white solid,
350.3 mg); Mp: 87.9-90.6 C; H NMR (400 MHz, CDCl3): δ
7.35 (t, J = 7.7 Hz, 1H), 7.12 (d, J = 7.7 Hz, 2H); 13C {1H} NMR
(100 MHz, CDCl3):δ 142.1, 132.0, 127.2, 117.2, 113.3, 20.7.
Terephthalonitrile (2m).22 Yield: 90% (white solid, 346.0
mg); Mp: 222.1-225.6 oC; 1H NMR (400 MHz, CDCl3): δ 7.81 (s,
4H); 13C {1H} NMR (100 MHz, CDCl3): δ 132.8, 117.0, 116.6.
Cinnamonitrile (2n) (100% E).8a Yield: 68% (colorless
liquid, 263.5 mg); 1H NMR (400 MHz, CDCl3): δ 7.94 – 7.31 (m,
1H), 5.89 (d, J = 16.7 Hz, 1H); 13C {1H} NMR (100 MHz,
CDCl3): δ 150.3, 133.3, 131.0, 128.9, 127.2, 118.0, 96.1.
3,7-Dimethyl-2,6-octadienenitrile (2o) (Z:E=1:1).6e Yield:
63% (yellowish liquid, 282.1 mg); H NMR (400 MHz, CDCl3):
δ 5.06 – 4.91 (m, 2H), 2.35 (td, J = 7.5, 2.2 Hz, 1H), 2.19 – 2.03
(m, 3H), 1.97 (dd, J = 2.4, 1.1 Hz, 2H), 1.87 – 1.80 (m, 1H), 1.66
– 1.48 (m, 6H); 13C {1H} NMR (100 MHz, CDCl3): δ 165.1,
164.9, 133.1, 132.9, 122.5, 117.2, 116.9, 95.9, 95.3, 38.5, 36.3,
26.2, 25.72, 25.68, 22.8, 20.9, 17.7.
o
1
Anisonitrile (2a).15 Yield: 95% (white solid, 379.5 mg); Mp:
60.1-61.9 oC; 1H NMR (400 MHz, CDCl3): δ 7.60 (d, J = 9.0 Hz,
2H), 6.95 (d, J = 9.0 Hz, 2H), 3.87 (s, 3H); 13C {1H} NMR (100
MHz, CDCl3): δ 162.8, 133.9, 119.2, 114.7, 103.9, 55.5.
4-tert-Butylbenzonitrile (2b).16 Yield: 95% (colorless liquid,
1
453.8 mg); H NMR (400 MHz, CDCl3): δ 7.63 – 7.56 (m, 2H),
7.52 – 7.45 (m, 2H), 1.33 (s, 9H); 13C {1H} NMR (100 MHz,
1
CDCl3):δ 156.4, 131.8, 126.0, 119.0, 109.1, 35.1, 30.7.
p-Phenylbenzonitrile (2c).16 Yield: 91% (white solid, 489.3
1
mg); Mp: 86.1-88.0 oC; H NMR (400 MHz, CDCl3): δ 7.72 (dd,
J = 19.0, 8.3 Hz, 4H), 7.60 (d, J = 7.1 Hz, 2H), 7.52 – 7.40 (m,
3H); 13C {1H} NMR (100 MHz, CDCl3): δ 145.4, 138.9, 132.4,
128.9, 128.5, 127.5, 127.0, 118.8, 110.6.
Acknowledgments
2-Naphthonitrile (2d).17 Yield: 90% (white solid, 413.6 mg);
1
Mp: 68.6-69.8 oC; H NMR (400 MHz, CDCl3): δ 8.25 (s, 1H),
We thank the National Natural Science Foundation of China
(No. 21672143) for the financial support.
7.92 (t, J = 8.9 Hz, 3H), 7.68 – 7.59 (m, 3H); 13C {1H} NMR
(100 MHz, CDCl3): 134.4, 134.0, 132.0, 129.0, 128.9, 128.3,
127.9, 127.5, 126.1, 119.2, 109.1.
Supplementary Material
4-Chlorobenzonitrile (2e).15 Yield: 90% (white solid, 371.4
mg); Mp: 91.2-94.7 C; H NMR (400 MHz, CDCl3): δ 7.65 –
7.58 (m, 2H), 7.51–7.44 (m, 2H); 13C {1H} NMR (100 MHz,
CDCl3):δ 139.5, 133.3, 129.6, 117.9, 110.7.
o
1
Supplementary data related to this article can be found at
References and notes
3-Chlorobenzonitrile (2f).18 Yield: 90% (white solid, 371.5
mg); Mp:38.9-41.1 oC; 1H NMR (400 MHz, CDCl3):δ 7.68 – 7.53
(m, 3H), 7.44 (t, J = 7.9 Hz, 1H); 13C {1H} NMR (100 MHz,
CDCl3):δ 135.2, 133.2, 131.7, 130.5, 130.3, 117.4, 113.9.
1. (a) Schümperli, M. T.; Hammond, C.; Hermans, I. ACS Catal.
2012, 2, 1108-1117. (b) Suresh, S.; Joseph, R.; Jayachandran, B.;
Pol, A. V.; Vinod, M. P.; Sudalai, A.; Sonawane, H. R.;
Ravindranathan, T. Tetrahedron 1995, 51, 11305-11318. (c)
Suzuki, K.; Watanabe, T.; Murahashi, S.-I. Angew. Chem., Int. Ed.
2008, 47, 2079-2081. (d) Diamond, S. E.; Tom, G. M.; Taube, H.
J. Am. Chem. Soc. 1975, 97, 2661-2664. (e) Merino, E. Chem.
Soc. Rev. 2011, 40, 3835-3853. (f) Gunanathan, C.; Ben-David,
Y.; Milstein, D. Science 2007, 317, 790-792. (g) Xin, B; Zhou, Q.;
Lu, T. Mini-Rev. Org. Chem. 2012, 9, 319-340.
4-Bromobenzonitrile (2g).19 Yield: 88% (white solid, 480.5
o
1
mg); Mp: 110.6-112.7 C; H NMR (400 MHz, CDCl3): δ 7.68–
7.62 (m, 2H), 7.58–7.51 (m, 2H); 13C {1H} NMR (100 MHz,
CDCl3):δ 133.3, 132.5, 127.9, 117.9, 111.1.
2. (a) Pollak, P.; Romeder, G.; Hagedorn, F.; Gelbke, H. P. Nitriles.
In Ullmann’s Encyclopaedia of Industrial Chemistry; Wiley-VCH:
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4-(Trifluoromethyl)benzonitrile (2h).20 Yield: 76% (white
solid, 390.2 mg); Mp: 37.8-41.2 oC; 1H NMR (400 MHz, CDCl3):
δ 7.85 – 7.80 (m, 2H), 7.79 – 7.75 (m, 2H); 13C {1H} NMR (100
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1
Mp: 49.9-53.3 oC; H NMR (400 MHz, CDCl3): δ 8.91 (dd, J =
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1.9 Hz, 1H), 7.50 – 7.42 (m, 1H); 13C {1H} NMR (100 MHz,
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1-Naphthonitrile (2j).16 Yield: 89% (white solid, 409.0 mg);
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125.1, 124.9, 117.8, 110.1.

6
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