Direct oxidative conversion of alcohols, aldehydes and amines into nitriles using hypervalent iodine(III) reagent

Article abstract of DOI:10.1055/s-0030-1258281

An efficient, facile, and high-yielding procedure for the direct oxidative conversion of alcohols, aldehydes, and primary, secondary, and tertiary amines into the corresponding nitriles using the hypervalent iodine(III) reagent hydroxy(tosyloxy)iodobenzene in combination with ammonium acetate as a nitrogen source is reported. The oxidation proceeded in mixed solvent to afford nitriles in excellent yields and high selectivity even at room temperature. Selective oxidation of primary amines in the presence of secondary amines and tertiary amines was also achieved. A possible mechanism for the oxidation is proposed.

Full text of DOI:10.1055/s-0030-1258281

PAPER
4235
Direct Oxidative Conversion of Alcohols, Aldehydes and Amines into Nitriles
Using Hypervalent Iodine(III) Reagent
O
xidation of Alc
h
A
ldeh
e
ydes, and
A
n
mines to
N
it
j
riles ie Zhu, Chengguo Sun, Yunyang Wei*
School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. of China
Fax +86(25)84317078; E-mail: ywei@mail.njust.edu.cn
Received 18 August 2010; revised 13 September 2010
of more than a stoichiometric amount of iodine, which
Abstract: An efficient, facile, and high-yielding procedure for the
direct oxidative conversion of alcohols, aldehydes, and primary,
secondary, and tertiary amines into the corresponding nitriles using
the hypervalent iodine(III) reagent hydroxy(tosyloxy)iodobenzene
in combination with ammonium acetate as a nitrogen source is re-
ported. The oxidation proceeded in mixed solvent to afford nitriles
in excellent yields and high selectivity even at room temperature.
Selective oxidation of primary amines in the presence of secondary
amines and tertiary amines was also achieved. A possible mecha-
nism for the oxidation is proposed.
could lead to the generation of excess amounts of salts as
byproducts during workup and the transformation of ali-
phatic compounds often gave unsatisfactory yields.
On the other hand, hypervalent iodine(III) reagents have
drawn considerable attention as mild and highly chemose-
lective oxidizing reagents for various organic transforma-
tions.24 As a result of their nontoxic nature, affordability,
and safety profile, hypervalent iodine(III) reagents are
nowadays popular reagents for the formation of carbon–
carbon bonds, carbon–heteroatom bonds, and hetero-
atom–heteroatom bonds. Activation of carbon–hydrogen
bonds, rearrangements, and fragmentations can be also in-
duced by these reagents. Therefore, hypervalent iodine
compounds offer high potential for the improvement of
known reactions, not only from an environmental point of
view, they are also potentially interesting reagents for the
development of completely new synthetic transforma-
tions.
Key words: alcohols, aldehydes, amines, hypervalent iodine, oxi-
dations
Nitriles are of considerable interest as an integral part of
dyes, herbicides, natural products, and pharmaceuticals.1
Moreover, the cyanide group plays a crucial role in organ-
ic synthesis as it can be easily converted into a variety of
functional groups, such as acids, amides, ketones, oximes,
and amines.2 The most typical synthetic procedure for the
preparation of nitriles is by nucleophilic displacement
from substrates containing suitable leaving groups, such
as alkyl halides.3 Other methods, such as by dehydration
of amides4 and aldoximes,5 have been traditionally em-
ployed to accomplish this transformation. The direct con-
version of alcohols,6 aldehydes,7 carboxylic acids,8
amines,9 azides,10 pyridine N-oxides,11 and boronic
acids,12 into nitriles has also been explored. Of the one-pot
preparative methods developed in recent years, the use of
ammonia combined with an appropriate oxidant, such as
in the following systems NH3/O2/CuCl2·H2O/MeONa,13
NH3/Pb(OAc)4,14 NH3/I2/MeONa,15 NH3/S8/NaNO2,16
NH3/H2O2/CuCl,17 NH3/I2,18 NH3/CAN,19 NH3/NBS,20
NH3/TBHP/KI(I2),6g or NH3/IBX,21 is considered to be an
expedient method for this transformation. However, am-
monia used as the nitrogen source in these procedures
may cause environmental problems because ammonia has
an undesirable smell and is a common and undesirable
contaminant in waste water and biomass cultivation me-
dia. The adverse effects of ammonia have promoted the
development of various techniques for its removal.22 Pre-
viously, ammonium acetate has also been developed, as a
good cyanide source in the system ammonium acetate/
iodine.23 One of the limitations of this procedure is the use
In continuation of our efforts to develop new applications
of hypervalent iodine compounds,25 herein, we would like
to report a facile procedure for the direct oxidation of al-
cohols, aldehydes, and amines to the corresponding
nitriles with [hydroxy(tosyloxy)iodo]benzene [HTIB,
PhI(OH)OTs, Koser’s reagent] using ammonium acetate
as the nitrogen source.
To the best of our knowledge, direct oxidative conversion
of an alcohol into the corresponding nitrile in one-pot
manner is extremely limited,6 and there is no report on the
use of hypervalent iodine(III) reagents as an oxidant for
the preparation of nitriles. The initial experiments were
carried out using 4-nitrobenzyl alcohol as the model sub-
strate (Table 1). Initially, a range of hypervalent iodine
reagents such as PhIO, PhICl2, PhIO2, PhI(OAc)2, and
HTIB were used as the oxidant in the reaction, it was
found that using PhI(OAc)2 and HTIB as the oxidant gave
4-nitrobenzonitrile in 17% and 36% yields, respectively
(entries 1–5). Encouraged by these results, we examined
the effects of nitroxyl radicals, 2,2,6,6-tetramethylpipe-
ridinyloxyl (TEMPO) and N-hydroxyphthalimide (NHPI),
on the reaction, with the aim of promoting the initial oxi-
dation of the alcohol to an intermediate aldehyde and thus
facilitating the formation of the final product. Fortunately,
TEMPO serves as a good catalyst and enhances the reac-
tion remarkably (entry 6); the catalytic activity of NHPI
was much lower (entry 8). Ammonium salts other than
ammonium acetate were also used as a nitrogen source,
SYNTHESIS 2010, No. 24, pp 4235–4241
x
x.
x
x
.
2
0
1
0
Advanced online publication: 30.09.2010
DOI: 10.1055/s-0030-1258281; Art ID: F14610SS
© Georg Thieme Verlag Stuttgart · New York

4236
C. Zhu et al.
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but lower yields were obtained (entries 9–11). Next, an in- In order to evaluate the versatility of this novel catalytic
vestigation of the effects of the solvent on the reaction system, we applied the procedure to the oxidation of a
showed that dichloromethane, chloroform, and ethyl wide range of alcohols (Table 2). Excellent chemoselec-
acetate were equally efficient for the reaction, whereas the tivity was observed with the optimized oxidation condi-
reaction did not proceed well using methanol or ethanol as tions. We detected no phenol oxidation products, which
the solvent (entries 12–16). These results demonstrated are known to form in reactions with aryl-l3-iodanes (entry
that protic solvents cannot be used as a solvent for this re- 5).26 Allylic alcohols such as cinnamyl alcohol (entry 6)
action, regardless of the polarity of the solvent. However, were also oxidized efficiently without any observable re-
the use of water as a co-solvent is beneficial to the reac- action at the double bond functionality. The electronic
tion, which may be explained by the improvement of the properties of the substituents in the aromatic ring had a re-
dissolution of ammonium acetate (entry 17). Addition of markable influence on the rate of the oxidation of benzyl
zinc oxide or 3Å molecular sieves to accelerate the dehy- alcohols. Strong electron-withdrawing groups, such as the
dration of in situ formed aldimines to nitriles in the reac- nitro group, improve the rate of the oxidation of the alco-
tion medium did not improve the reaction (entries 18 and hol (entry 2). Strong electron-donating groups, such as
19). It is noteworthy that the reaction can also proceed methoxy, lowered the reaction rate (entry 3). This differs
smoothly even at room temperature, albeit a longer reac- from previously reported procedures, where the methoxy
tion time was required (entry 20).
group favors the oxidation of the alcohol.6g It is worth
Table 1 Optimization Studies for the Conversion of 4-Nitrobenzyl Alcohola
CN
OH
oxidant, catalyst, NH4X
additive, solvent, temp
O2N
O2N
Entry
1
Oxidant
PhIO
NH4X
Solvent
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
EtOH
Catalyst
–
Additive
Temp (°C)
80
Yield (%)
–
NH4OAc
NH4OAc
NH4OAc
NH4OAc
NH4OAc
NH4OAc
–
–
2
PhCl2
PhIO2
PhI(OAc)2
HTIB
HTIB
HTIB
HTIB
HTIB
HTIB
HTIB
HTIB
HTIB
HTIB
HTIB
HTIB
HTIB
HTIB
HTIB
HTIB
–
–
80
–
3
–
–
80
–
4
–
–
80
17
5
–
–
80
36
6
TEMPO
TEMPO
NHPI
–
80
91
7
–
80
82b
46
8
NH4OAc
NH4Cl
–
80
9
TEMPO
TEMPO
TEMPO
TEMPO
TEMPO
TEMPO
TEMPO
TEMPO
TEMPO
TEMPO
TEMPO
TEMPO
–
80
27
10
11
12
13
14
15
16
17
18
19
20
NH4HCO3
HCO2NH4
NH4OAc
NH4OAc
NH4OAc
NH4OAc
NH4OAc
NH4OAc
NH4OAc
NH4OAc
NH4OAc
–
80
–
–
80
58
–
80
<10
<10
81
MeOH
CH2Cl2
CHCl3
EtOAc
MeCN
MeCN
MeCN
MeCN
–
80
–
80
–
80
78
–
80
85
H2O
ZnO
3 Å MS
H2O
80
96c
87
80
80
90
r.t.
92d
a Reactions conditions: 4-nitrobenzyl alcohol (1 mmol), oxidant (2.5 mmol), NH4X (10 mmol), catalyst (0.2 mmol), solvent (4 mL), 80 °C, 3 h,
unless otherwise noted.
b Yield of 4-nitrobenzaldehyde.
c H2O (1 mL) was added.
d Reaction was carried out at r.t. for 24 h.
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Oxidation of Alcohols, Aldehydes, and Amines to Nitriles
4237
mentioning that, together with the good results with ben- dehydes into nitriles did not need the presence of TEMPO,
zylic alcohols, the yields obtained from the oxidation of and proceeded faster than the oxidation of alcohols under
aliphatic alcohols under the same conditions are also quite similar conditions.
high (entries 8–10). In view of the fact that the oxidation
of aliphatic alcohols is much more difficult than the oxi-
dation of benzylic alcohols, results obtained with this pro-
Table 3 Oxidation Conversion of Aldehydes into Nitriles with
HTIB/NH4OAca
cedure were very satisfactory.
Entry Substrate
Product
Time Yieldb
(h)
(%)
Table 2 Oxidation Conversion of Alcohols into Nitriles with HTIB/
TEMPO/NH4OAca
CHO
CN
1
2
2
98
Entry Substrate
Product
Time Yieldb
(h)
(%)
CN
CHO
2
2
97
93
CN
OH
1
3
95
O2N
NO2
O2N
NO2
CN
CN
CHO
CN
OH
OH
3
2
3
5
3
5
96
90
95
88
O2N
O2N
CHO
CHO
CHO
CHO
CHO
CN
3
4
5
6
7
4
2
2
4
90
96
95
86
MeO
MeO
Cl
MeO
Br
MeO
Br
CN
CN
OH
4
Cl
CN
CN
CN
OH
OH
5
HO
HO
Cl
Cl
CN
6
4
90
HO
HO
CN
7
3
4
91
87
OH
8
3
92
CN
O
O
OH
CN
8
9
2
3
90
91
CN
CHO
CHO
O
O
9
Me(CH2)6CH2OH
Me(CH2)10CH2OH
Me(CH2)6CN
Me(CH2)10CN
5
5
85c
81c
CN
10
10
a Reaction conditions: alcohol (1 mmol), HTIB (2.5 mmol), TEMPO
(0.2 mmol), NH4OAc (10 mmol), MeCN–H2O (4:1, 5 mL), 80 °C.
b Yields of isolated products unless otherwise noted.
c Yields were determined by GC.
11
12
Me(CH2)6CHO
Me(CH2)10CHO
Me(CH2)6CN
Me(CH2)10CN
4
4
90c
88c
CHO
CN
13
4
86c
The oxidation of alcohols to nitriles using HTIB/TEMPO/
NH4OAc is believed to proceed via the intermediate for-
mation of aldehydes (Table 1, entry 7). Further studies
show that structurally diverse aldehydes, including ben-
zylic, allylic, heterocyclic, and aliphatic aldehydes, can
also be smoothly oxidized to the corresponding nitriles in
excellent yield with the HTIB/NH4OAc system in the
absence of TEMPO (Table 3). 2-Ethylhexanal, an a-
branched aliphatic aldehyde, was also oxidized to 2-ethyl-
hexanenitrile efficiently (entry 13). The effect of the elec-
tronic nature of the aldehyde was similar to that found in
the oxidation of alcohols. Additionally, steric hindrance
had a relatively minor influence on the oxidation of alde-
hydes (entries 2 and 3). As expected, the conversion of al-
a Reaction conditions: aldehyde (1 mmol), HTIB (1.5 mmol),
NH4OAc (10 mmol), MeCN–H2O (4:1, 5 mL), 80 °C.
b Yields of isolated products unless otherwise noted.
c Yields were determined by GC.
To demonstrate the scope and efficiency of this method,
the HTIB/NH4OAc system was extended to the direct
conversion of primary, secondary, and tertiary amines
into the corresponding nitriles. As shown in Table 4, most
amines underwent oxidation to afford the corresponding
nitriles in excellent yields. This transformation can also
proceed without ammonium acetate (entry 1). Diamines
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4238
C. Zhu et al.
PAPER
were also converted into the corresponding dinitriles in amine gave 81% conversion of benzylamine and less than
good yields (entries 8 and 9). When N-methyl secondary 10% conversion of N,N-dimethylbenzylamine, respec-
amines and N,N-dimethyl tertiary amines were treated tively (entry 2). These results suggest that chemoselective
with HTIB under the same conditions, the corresponding oxidation of primary amine in the presence of secondary
nitriles could be again obtained in good yields (entries 10– and tertiary amine is possible with the present system.
12).
Table 5 Competitive Oxidation of Primary, Secondary, and Tertia-
ry Aminesa
Table 4 Oxidation Conversion of Amines into Nitriles with HTIB/
NH4OAca
Entry
Substrate
Time (h)
Conversionb (%)
Entry Substrate
Product
Time Yieldb
(h) (%)
NH2
CN
1
3
3
84 (73c)
94
76
<10
NH2
+
1
2
Me
CN
CN
N
H
NH2
2
O2N
O2N
NH2
NH2
3
5
83
81
<10
+
2
3
2
2
MeO
MeO
CN
Me
NH2
N
4
3
3
92
82
Me
Cl
Cl
O
Me
5
N
H
NH2
NH2
CN
O
57
36
+
CN
6
4
5
3
75
Me
Me
N
7
8
Me(CH2)10CH2NH2
Me(CH2)10CN
72d
90e
a The reactions were carried out on a 1:1 mixture of primary, second-
ary, and tertiary amines.
H2N
NH2
CN
CN
b Conversion was based on the yield of product by column chromatog-
raphy isolation.
67e
NH2
NH2
CN
CN
9
10
11
12
5
3
3
3
CN
CN
CN
Based on these results, a plausible reaction pathway for
the conversion of alcohols, aldehydes and amines into the
corresponding nitriles is depicted in Scheme 1. For the
conversion of a primary alcohol into the corresponding ni-
trile, TEMPO served as the actual oxidant to oxidize the
alcohol to the corresponding aldehyde, the role of HTIB is
to regenerate TEMPO from TEMPOH. Then, the alde-
hyde reacts with ammonium acetate to form an aldimine,
which undergoes oxidation by HTIB to afford the
N-I(OTs)Ph aldimine. Elimination of HOTs from the
N-I(OTs)Ph aldimine gives the final nitrile product. Iodo-
benzene was detected at the end of the reaction. The oxi-
dation of an amine with HTIB produces the imine
initially,27 which is subsequently hydrolyzed to give an al-
dehyde, further oxidation of the aldehyde will yield a ni-
trile; aldehyde was detected in the reaction. Another route
B not via an aldehyde is also possible, since nitriles were
also obtained from the reaction of an amine and HTIB
without the presence of ammonium acetate (Table 4, entry
1, 10, and 12).
Me
82 (39c)
80
N
H
H
N
Me
N
78 (22c)
Me
a Reaction conditions: amine (1 mmol), HTIB (2.5 mmol), NH4OAc
(10 mmol), MeCN–H2O (4:1, 5 mL), 80 °C.
b Yields of isolated products unless otherwise noted.
c NH4OAc was not used.
d Yields were determined by GC.
e Double amount of HTIB was used.
Table 5 shows the results of the competitive oxidation of
primary, secondary, and tertiary amines. The competing
oxidation of an equimolar mixture of benzylamine and N-
methylbenzylamine into benzonitrile resulted in 76% con-
version of benzylamine and less than 10% conversion of
N-methylbenzylamine (entry 1). Oxidation of an equimo-
lar mixture of benzylamine and N,N-dimethylbenzyl-
In conclusion, a simple and efficient method for the con-
version of alcohols, aldehydes, primary, secondary, and
Synthesis 2010, No. 24, 4235–4241 © Thieme Stuttgart · New York

PAPER
Oxidation of Alcohols, Aldehydes, and Amines to Nitriles
4239
R1
C
N
I
R1CH2OH
N
O
PhI(OH)OTs
PhI
– PhI
– HOTs
NH4OAc
OTs
Ph
PhI(OH)OTs
– H2O
R1CHO
R1
C
H
N
R1 CH NH
N
– H2O
OH
H2O
A
PhI(OH)OTs
– R2OH
B
H
– PhI
PhI(OH)OTs
– R2OH
R1-CH=NR2
R1-CH2-NR2
R1-CH-NR2
2
– HOTs
I
Ph
OTs
R1 = aryl, alkyl; R2 = H, Me
Scheme 1 Plausible reaction pathway for the formation of nitriles
Oxidation of Amines with HTIB/NH4OAc; General Procedure
To a soln of amine (1 mmol) and NH4OAc (0.77 g, 10 mmol) in
MeCN–H2O (4:1, 5 mL) was added HTIB (0.95 g, 2.5 mmol). The
mixture was stirred at 80 C for several hours (GLC or TLC moni-
toring). After completion, the mixture obtained was treated as above
to afford the corresponding pure product.
tertiary amines into the corresponding nitriles with HTIB
using ammonium acetate as the nitrogen source has been
developed. A key feature of the oxidation protocol is its
inherent simplicity. There is no need for rigorous exclu-
sion of air or moisture in order to effect a clean oxidation,
the reaction conditions and reagents are easy to handle
and the reaction is applicable to various kinds of alcohols,
aldehydes, and amines.
Benzonitrile
IR (KBr): 2218 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.45–7.65 (m, 5 H, Ar).
All chemicals (AR grade) were obtained from commercial sources
and used without further purification. H NMR spectra were ob-
4-Chlorobenzonitrile
1
IR (KBr): 2237 cm–1.
tained with TMS as internal standard in CDCl3 using a Bruker DRX
300 (300MHz) spectrometer. Gas chromatography (GC) analysis
was performed on an Agilent GC-6820 chromatograph equipped
with a 30 m × 0.32 mm × 0.5 mm HP-Innowax capillary column and
a flame ionization detector. GC-MS spectra were recorded on
Thermo Trace DSQ GC-MS spectrometer using a TRB-5MS (30
m × 0.25 mm × 0.25 mm) column. IR spectra were recorded on a
Shimadzu spectrophotometer using KBr discs. Melting points were
determined on a Yamato melting point apparatus Model MP-21.
Progress of the reactions was followed by TLC (silica gel poly-
grams SIL G/UV 254 plates). Column chromatography was per-
formed using Silicycle (40–60 mm) silica gel.
1H NMR (300 MHz, CDCl3): d = 7.67 (d, J = 8.1 Hz, 2 H, Ar), 7.52
(d, J = 8.1 Hz, 2 H, Ar).
4-Nitrobenzonitrile
IR (KBr): 2230 cm–1.
1H NMR (300 MHz, CDCl3): d = 8.42 (d, J = 8.4 Hz, 2 H, Ar), 7.95
(d, J = 8.4 Hz, 2 H, Ar).
4-Methoxybenzonitrile
IR (KBr): 2218 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.57 (d, J = 8.7 Hz, 2 H, Ar), 6.94
(d, J = 8.7 Hz, 2 H, Ar), 3.85 (s, 3 H, OCH3).
Oxidation of Alcohols with HTIB/TEMPO/NH4OAc;
General Procedure
Cinnamonitrile
To a soln of alcohol (1 mmol), NH4OAc (0.77 g, 10 mmol), and
TEMPO (0.03 g, 0.2 mmol) in MeCN–H2O (4:1, 5 mL) was added
HTIB (0.95 g, 2.5 mmol). The mixture was stirred at 80 °C for sev-
eral hours (GLC or TLC monitoring). After completion, aq
NaHCO3 and EtOAc were sequentially added to the residue and
then the mixture was stirred vigorously for 10 min. The organic lay-
er was separated, and the aqueous layer was extracted with EtOAc.
The combined EtOAc phases were concentrated under vacuum. The
crude product was purified by column chromatography (petroleum
ether–EtOAc, 10:1) to provide analytically pure product (1H NMR
and GC/MS).
IR (KBr): 2223 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.38–7.43 (br s, 6 H, Ar, PhCH),
5.87 (d, J = 16.5 Hz, 1 H, CHCN).
Benzyl Cyanide
IR (KBr): 2250 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.27–7.34 (m, 5 H, Ar), 3.67 (s, 2
H, CH2).
Supporting Information for this article is available online at
http://www.thieme-connect.com/ ejournals/toc/synthesis.
Oxidation of Aldehydes with HTIB/NH4OAc;
General Procedure
To a soln of aldehyde (1 mmol) and NH4OAc (0.77 g, 10 mmol) in
MeCN–H2O (4:1, 5 mL) was added HTIB (0.57 g, 1.5 mmol). The
mixture was stirred at 80 °C for several hours (GLC or TLC moni-
toring). After completion, the mixture obtained was treated as above
to afford the corresponding pure product.
Acknowledgment
We are grateful to Nanjing University of Science and Technology
for financial support.
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C. Zhu et al.
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