Direct synthesis of nitriles from cleavage of C=C double bond with nitrite as the nitrogen source and oxidant

Article abstract of DOI:10.1016/j.tetlet.2016.04.108

The transformation of the C=C bond of olefin to nitriles has been developed, using easily available NaNO₂ as both the nitrogen source and oxidant. Several aryl, heterocyclic nitriles with various substituting groups could be successfully prepared in good to high yields. Based upon experimental observations, a possible reaction mechanism is proposed.

Full text of DOI:10.1016/j.tetlet.2016.04.108

Accepted Manuscript
Direct synthesis of nitriles from cleavage of C=C double bond with nitrite as the
nitrogen source and oxidant
Qiang Liu, Bao Fang, Xiaohui Bai, Yuan Liu, Yao Wu, Guiming Xu, Cancheng
Guo
PII:
S0040-4039(16)30491-9
DOI:
http://dx.doi.org/10.1016/j.tetlet.2016.04.108
TETL 47608
Reference:
To appear in:
Tetrahedron Letters
Received Date:
Revised Date:
Accepted Date:
8 March 2016
27 April 2016
29 April 2016
Please cite this article as: Liu, Q., Fang, B., Bai, X., Liu, Y., Wu, Y., Xu, G., Guo, C., Direct synthesis of nitriles
from cleavage of C=C double bond with nitrite as the nitrogen source and oxidant, Tetrahedron Letters (2016), doi:
http://dx.doi.org/10.1016/j.tetlet.2016.04.108
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Direct synthesis of nitriles from cleavage of C=C double bond with nitrite as the nitrogen source
and oxidant
Qiang Liu, BaoFang,XiaohuiBai, Yuan Liu, Yao Wu, GuimingXu, CanchengGuo*

Tetrahedron Letters
1
Tetrahedron Letters
Direct synthesis of nitriles from cleavage of C=C double bond with nitrite as the
nitrogen source and oxidant
Qiang Liu, Bao Fang, Xiaohui Bai, Yuan Liu, Yao Wu, Guiming Xu, Cancheng Guo*
College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China
*
Corresponding author. Tel.: +86-731-88821488; fax: +86-731-88821667; e-mail: ccguo@hnu.edu.cn
A RT ICL E INFO
A BST RA CT
Article history:
Received
The transformation of the C=C bond of olefin to nitriles has been developed, using easily
available NaNO as both the nitrogen source and oxidant. Several aryl, heterocyclic nitriles
2
Received in revisedform
with various substituting groups could be successfully prepared in good to high yield. Based
Accepted
upon experimental observations, a possible reaction mechanism is proposed.
Available online
2
015 Elsevier Ltd. All rights reserved.
Keywords:
Synthesis
C=C cleavage
Olefins
Nitriles
NaNO
2
Nitriles are widely used in synthetic organic chemistry,
chemical industry as well as biological applications, as they serve
as important building blocks in the pharmaceutical, fine
conversion involves an oxidant and a nitrogen source. In this
respect, exploring a reagent served as the nitrogen source and
oxidant remains a challenge in this promising field. Very
recently, Ge’s firstly reported the synthesis nitriles from
2
ketones and aldehydes using NaNO as the nitrogen source and
oxidant. Inspired by these results, herein, we present a novel
pathway to convert the C=C bond of aromatic olefins to a C≡N
1
14
chemical, dye, and agrochemical industries . Traditionally, these
2
nitriles are synthesized by metal cyanides-catalyzed cyanation of
3
4
alkyl and aryl halides, Sandmeyer reaction or ammoxidation of
aromatic hydrocarbons on a bulk scale, in which highly toxic
cyanide containing reagent or drastic conditions are required.
2
bond in present of NaNO and HCOOH (Scheme 1c). Utilizing
5
6
7
8
9
10
Apart from C-X bond, C-O, C-N, C-C, C-H, C=O, C=N,
NaNO as the oxidant as well as the nitrogen source avoids
2
1
1
and C≡C bonds were also found to be converted successfully to
C≡N bond with relatively low toxic nitrogen sources. Our group
has also developed some direct conversions from C=O bond of
highly toxic cyanides, expensive transition metals and reduces
waste disposal.
Previous work
aromatic ketones into nitriles using (NH
4
)
2
CO
3
as the nitrogen
N
O
R
TEMPO, O2
TMSN3
9
a
source in the presence of molecular oxygen . Alkenes are also
easily available and inexpensive function groups. For the sake of
overcoming the shortcoming of using toxic HCN, Morandi
a)
R
N
1
2
R2
et.al. report a nickel-catalyzed transfer retro-hydrocyanation
reaction of alkenes producing anti-Markovnikov nitrile products
with equivalent alkene byproducts. Meanwhile, some novel
approaches to nitriles through C=C bond cleavage has witnessed
PhI(OAc)2, NH4HCO3
R1
R1
R1
b)
c)
N
R2 AlCl ,NaNO
3
2
R1
1
3
O
stupendous growth of nitriles preparation in past decades. Jiao
7
a, 11a, 13a
et.al.
,2,6,6-tetramethylpiperidine-1-oxyl(TEMPO)-catalyzed
transformation of cyclic alkenes to nitriles using
trimethylsilylazide (TMSN ) as nitrogen source with oxygen as
successfully achieved the transition metal free
This work
d) R1
2
N
R2
NaNO2, H+
R1
3
Scheme 1. Approaches for the conversion of C=C to C≡N
an oxidant (Scheme 1a). The direct transformation of styrenes to
aromatic nitriles in the presence of N-bromosuccinimide (NBS),
Cu(OAc) and K CO was also achieved by the same group.
2 2 3
Obviously, the scope of the reaction appeared quite limited. In
order to overcome this problem, we report a metal-free
nitrogenation reaction of terminal and internal aromatic alkenes
through C=C bond cleavage using phenyliodoniumdiacetate
The initial survey of the reaction conditions was performed with
styrene (1a) as a model substrate, and the results are summarized
in Table 1. It was found that both acid and NaNO2 were
indispensable to the reaction (Table 1, entries 1 and 2). To our
delight, styrene could be converted into benzonitrile (2a) in 61.2
yield when the reaction was carried out with 3.75 equiv. of
2
NaNO and 0.5 mL (10 mmol) of HCOOH in acetonitrile at 70 C
1
3b
%
(
PIDA) as the oxidizing agent and NH
4
HCO
3
as nitrogen source
o
1
3c
(Scheme 1b).
Despite these developments, all of these

2
for 4h (Table 1, entry 3). Increasing the amount of NaNO
equiv., the yield of 2a increased to 84.1 % (Table 1, entries 3-5).
Unlike Lewis acid such as AlCl that could promote oxidative
amination of ketones and aldehydes into nitriles , relative weak
Brønsted acids such as formic acid facilitated the nitrogenation of
olefins (Table 1, entries 4, 6 and 7). On the contrary, the strong
2
to 5
halide at different positions (o-, m-, and p-) could influence the
conversion of C=C bond to C≡N bond. Styrenes with halogens
on para position of the phenyl ring favored the conversion of
C=C bond to C≡N bond (Table 2, 1i-1k). Styrene derivatives
bearing electron donating substituents provided the desired
benzonitriles in 70%-89% (Table 2, 1b-1h and 1r). Similar to the
reaction reported by our group , sterically hindered substrates
like 1,3,5-trimethyl-2-vinylbenzene showed good yield in the
optimized conditions (Table 2, 1e). The reaction of internal
alkenes, such as 3-phenylprop-2-en-1-ol, 3-chloro-1-phenyl-1-
propene, and 1-methoxy-4-(2-phenylethenyl)benzene were
sluggish under the optimized conditions (Table 2, 1v-1x).
Nitrogenation of the aliphatic alkenes was still problematic
(Table 2, 1u).
3
1
4
1
3c
acid such as CF
TsOH) was unable to improve yields of desired product 2a
Table 1, entries 8-10). The amount of HCOOH was increased to
.5 mL, the 2a yield reached highest (Table 1, entries 4 and 11,
2). The 2a yield did not enhanced with the increase of reaction
3
COOH, H
3
PO
4
and p-toluenesulfonic acid (p-
(
0
1
o
temperature, 70 C was the optimal temperature (Table 1, entries
, 13, 14). Further investigation showed this reaction was not air
4
or moisture sensitive and could be run under open air (Table 1,
entries 4) or under nitrogen (Table 1, entry 15) with similar
a,b
Table 2. The substrate scope of this transformation
yields, indicating that not atmospheric oxygen but NaNO
the oxidant. Using strong polar solvents such as CH CN, DMF,
EtOH, dioxane and EtOAc showed moderate to high yield of 2a
Table 1, entries 4, 16, 18-20), while using weak polar solvent,
such as toluene and CH ClCH Cl, gave low yields (Table 1,
2
was
N
R2
3
HCOOH
R1
R1
+ NaNO2
CH3CN,
(
1
2
Substrate
Product Substrate
Product
/%
2
2
/%
entries 21, 22). It is worthing to note that using DMSO as a polar
solvent gave low yield of 2a (Table 1, entry 17). Further
investigation indicated that DMSO participated in the reaction
with 1a, giving 45.5% yield of 2-(methylsulfonyl)-1-
phenylethanone oxime as major product (see Supporting
Information). Eventually, the conditions described in entry 4
were chosen as the standard conditions for furtherstudy.
Br
1
a
84 (2a)
1m 84 (2m)
Br
1b
8
7 (2b)
1n
78 (2n)
1
c
71 (2c)
76 (2d)
83 (2e)
1o
1p
1q
89 (2o)
95 (2p)
84 (2q)
F
a
Table 1. Screening of the reaction conditions.
1d
N
ClH2C
O2N
H+
1e
+
NaNO2
solvent, T, 4h
1a
2a
+
o
b
Entry NaNO
equiv
2
H
Solvent
T/ C Yield
/%
/
1f
89 (2f)
O
1r
88 (2r)
1
-
HCOOH
CH
3
CN
70
0
O
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
5
3.75
5
7.5
5
5
5
5
5
5
5
5
5
5
5
5
5
-
CH
CH
CH
CH
CH
3
3
3
3
3
3
3
3
3
3
3
3
3
3
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
70
70
70
70
70
70
70
70
70
70
70
80
50
70
70
70
70
70
70
70
70
0
HCOOH
61.2
84.1
80.2
75.8
74.6
24.4
19.2
27.2
66.3
50.3
76.3
47.0
82.5
46.4
18.8
39.3
40.4
46.9
16.4
17.3
1
h
86 (2g)
85 (2h)
85(2i)
1s
1t
1u
81 (2s)
76 (2t)
HCOOH
HCOOH
CH
CH
CF
H
P-TsOH
HCOOH
HCOOH
HCOOH
HCOOH
HCOOH
HCOOH
HCOOH
HCOOH
HCOOH
HCOOH
HCOOH
HCOOH
MeO
EtO
3
HCOOH
CH
1i
S
3
2
COOH CH
3
COOH
CH
CH
CH
CH
CH
CH
CH
CH
DMF
DMSO
EtOH
Dioxane
EtOAc
Toluene
3
PO
4
1j
1k
1l
Trace (2u)
41 (2a)
36 (2a)
0
1
2
Cl
Cl
c
c
d
60 (2j)
51 (2k)
OH
1v
3
4
5
6
7
8
9
0
1
2
c
Cl
1w
e
Cl
OCH3 1xc 20 (2a)
17 (2g)
1m
91(2l)
5
5
5
5
Br
2
2 2
CH ClCH Cl
a
Unless otherwise noted, the reaction was carried out with 1a (0.4 mmol),
acid (0.5 mL), and solvent (4.5 mL), heated and stirred for 4h in air.
a
Unless otherwise noted, the reaction was carried out with 1a (0.4 mmol),
o
2 3
NaNO (5 equiv.), HCOOH (0.5 mL), and CH CN (4.5 mL), 70 C, 4h, open
b
Determined by GC using p-dichlorobenzeneas the internal standard.
HCOOH (0.4 mL). HCOOH (0.6 mL). N
b
c
o
c
d
e
air. Isolated yield. Conditions: 80 C,8h.
2
To explore the mechanism of this conversion, some control
experiments were carried out. When styrene reacted under the
standard conditions, besides 84% yield of benzonitrile,
benzaldehyde, acetophenone, benzoic acid and (E)-β-nitrostyrene
were also detected by GCMS (Scheme 2a). When the
With optimized reaction condition in hand, we next examined
its substrate scope with various aryl, heterocyclic alkenes. The
results were summarized in Table 2. A variety of styrenes and 2-
vinylthiophene underwent nitrogenation reactions to afford the
corresponding nitriles in good to excellent yields. Styrene
derivatives with electron-withdrawing group performed the
reaction in 50%-95% yield (Table 2, 1i-1q), halide substituents
that can be used in subsequent coupling reactions were tolerated
o
temperature decreased to 25 C, 65% yield of α-nitro-ketoxime
were also found in 50min (Scheme 2b). Maybe one of
benzaldehyde, acetophenone, benzoic acid, (E)-β-nitrostyrene
and α-nitro-ketoxime was the important intermediate of this
1
5
in the reaction (Table 2, 1i-1n). However, styrenes bearing

Tetrahedron Letters
3
reaction. In view of this, a series experiments (Scheme 2c, 2d)
were performed to verify the hypothesis. The substrates (E)-β-
nitrostyrene was tested, affording trace desired benzonitrile,
whereas, using other possible carbonyl intermediates such as
benzaldehyde, acetophenone and benzoic acid as the substrate,
we could not detect benzonitrile at all (Scheme 2c). The
results suggested that this nitrogenation reaction did not proceed
via a carbonyl intermediates, which were proved to be easily
made this process simple, easy to operate, economical and eco-
friendly. The optimized synthetic system tolerated various
functional groups. Mechanistic studies revealed that the α-nitro-
ketoxime and 1-phenylglyoxal dioxime might be an intermediate
in this conversion through the nitrogenation of the C=C bond.
Further investigations on expanding the reaction scope and the
application of this transformation are currently ongoing in our
laboratory.
9
converted to nitriles . In contrast, the substrate α-nitro-ketoxime
Acknowledgment
could better achieve the conversion of the C=C bond to the C≡N
bond under the standard conditions with 89 % yield of desired
benzonitrile (Scheme 2d), and 1-phenylglyoxal dioxime
was simultaneously detected by GCMS through monitoring this
reaction. Then we used 1-phenylglyoxal dioxime as the substrate,
the yield of benzonitrile reached 86% under the standard
conditions (Scheme 2e). These experimental evidence supported
that styrene should complete the reaction of the C=C bond to the
C≡N bond through the intermediate α-nitro-ketoxime and 1-
phenylglyoxal dioxime.
We are grateful for the financial support from the National
Natural Science Foundation of China (21372068, 21572049),
Science and Technology Program of Hunan Province, China
(2014GK3115) and Science and Technology Program of
Changsha, China (K1508004-11).
Supplementary Data
Supplementary data associated with this article can be found in
the online version at
O
N
CHO
+
COOH
NO2
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5
9732.

Tetrahedron Letters
5
Highlights

A novel synthesis of aromatic nitriles from
aromatic olefins
Using cheap and widely available NaNO2 as the
oxidant and nitrogen source
The reaction proceeds smoothly under mild
conditions in good to excellent yields




Relative good functional group tolerance
A new oxidative nitrogenation mechanism was
proposed