Oxoammonium salt-mediated oxidative nitriles synthesis from aldehydes with ammonium acetate

Article abstract of DOI:10.1016/j.tetlet.2017.11.002

An efficient and scalable route for the synthesis of nitriles was developed by oxoammonium salt (4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate) mediated oxidative conversion of aldehydes with NH₄OAc. A variety of aliphatic aldehydes as well as benzaldehydes were converted into the corresponding nitriles in high yields. The nitroxyl radical which is the reduced species of the used oxoammonium salt was recovered by simple acid-base extraction for the recycling.

Full text of DOI:10.1016/j.tetlet.2017.11.002

Accepted Manuscript
Oxoammonium Salt-Mediated Oxidative Nitriles Synthesis from Aldehydes
with Ammonium Acetate
Myeong Jin Kim, Junyoung Mun, Jinho Kim
PII:
S0040-4039(17)31396-5
https://doi.org/10.1016/j.tetlet.2017.11.002
TETL 49445
DOI:
Reference:
Tetrahedron Letters
To appear in:
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Revised Date:
Accepted Date:
11 September 2017
27 October 2017
2 November 2017
Please cite this article as: Kim, M.J., Mun, J., Kim, J., Oxoammonium Salt-Mediated Oxidative Nitriles Synthesis
from Aldehydes with Ammonium Acetate, Tetrahedron Letters (2017), doi: https://doi.org/10.1016/j.tetlet.
2017.11.002
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Tetrahedron Letters
Oxoammonium Salt-Mediated Oxidative Nitriles Synthesis from Aldehydes with
Ammonium Acetate
Myeong Jin Kima, Junyoung Munb, , Jinho Kima, 
aDepartment of Chemistry, Incheon National University, 119 Academy-ro, Yeonsu-gu, Incheon 22012, Republic of Korea
bDepartment of Energy and Chemical Engineering, Incheon National University, 119 Academy-ro, Yeonsu-gu, Incheon 22012, Republic of Korea
ARTICLE INFO
ABSTRACT
Article history:
Received
An efficient and scalable route for the synthesis of nitriles was developed by oxoammonium salt
(4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxoammonium
tetrafluoroborate)
mediated
Received in revised form
Accepted
Available online
oxidative conversion of aldehydes with NH4OAc. A variety of aliphatic aldehydes as well as
benzaldehydes were converted into the corresponding nitriles in high yields. The nitroxyl radical
which is the reduced species of the used oxoammonium salt was recovered by simple acid-base
extraction for the recycling.
Keywords:
oxoammonium salt
nitriles
2009 Elsevier Ltd. All rights reserved.
ammonium acetate
oxidation
organic synthesis
The nitrile moiety is a highly important functional group in
organic synthesis, because it could be employed as a versatile
intermediate for the synthesis of various functional groups as
well as heterocycles.1 Besides, the nitrile moiety itself plays a
crucial role in numerous fruitful compounds such as
pharmaceuticals, agrochemicals, and functional materials.2 The
most traditional methods for the preparation of nitriles are
substitution reactions3 such as Sandmeyer reaction4 and
Rosenmund-von Braun reaction5 using metal cyanide. In order to
avoid the use of toxic metal cyanides, several organic cyanide
hydroxyl amines.12 In metal-free conditions, the oxoammonium
salt acts as an oxidant and the hydroxyl amine is produced (two-
electrons redox).13 On the other hand, it was proposed that the
one-electron redox between the nitroxyl radical and the hydroxyl
amine facilitated the oxidation in the presence of transition metal
co-catalyst such as Cu.14 The redox system between
oxoammonium salts and hydroxyl amines is attractive because
they are metal-free and recyclable.15 In addition, these systems
provide highly selective oxidations under mild conditions.
Therefore, diverse oxidative transformations such as alcohol
oxidation, amine oxidation, oxidative esterification, oxidative
cleavage of ether, cross dehydrogenative coupling (CDC
reaction), silyl enol conversion, and cyclodiene synthesis have
been accomplished stoichiometrically16 or catalytically.17
However, few examples of metal-free aldehydes to nitriles
transformations mediated by oxoammonium salt were
reported.18,19
sources
have
been
investigated.6
Functional
group
transformations from nitrogen-containing functionalities to
nitriles are another pathways that no direct incorporation of
cyano groups are necessary. Such transformations are including
double oxidation of primary amines7 and dehydration of amides8
or aldoximes.9 These approaches sometimes require hash reaction
conditions and showed several limitations in substrate scope and
scalability. Recently, the oxidative transformations of aldehydes
or alcohols with a nitrogen source have received much attention.
A variety of oxidants including (n-Bu4N)2S2O8, I2, NaICl2,
PhI(OH)OTs have been stoichiometrically employed for the
synthesis of nitriles.10 In addition, aerobic oxidative nitrile
synthesis using oxygen as a terminal oxidant have been
developed,11 although the safety issue should be considered in
plant scale.
In 2015, Bailey and Leadbeater et al. reported that 4-
acetamido-2,2,6,6,-tetramethylpiperidine-1-oxoammonium
-
tetrafluoroborate (4-AcNH-TEMPO+BF4 , Bobbitt’s Salt)
mediated oxidative nitriles synthesis from aldehydes and alcohol
using hexamethyldisilazane (HMDS) (Scheme 1, A).18a Although
this protocol showed good substrate scope and functional group
tolerance in mild conditions, the requirement of toxic HMDS as a
nitrogen source made this protocol less attractive. In 2016, Shen
group developed an oxidative aldehydes to nitriles transformation
using catalytic amount of 2,2,6,6,-tetramethylpiperidine-N-oxyl
Oxoammonium salts are interesting oxidants with three
o—xi—dati—on states; oxoammonium salts, nitroxyl radicals, and
 Corresponding author. Tel.: +82-32-835-8876; fax: +82-32-835-4866; e-mail: jymoon@inu.ac.kr (J. Mun)
 Corresponding author. Tel.: +82-32-835-8218; fax: +82-32-835-0762; e-mail: jinho@inu.ac.kr (J. Kim)

2
Tetrahedron
(TEMPO), but the use of HMDS was still required (Scheme 1,
We examined oxoammonium salt-mediated oxidative nitriles
synthesis with octanal as a model substrate (Table 1). First of all,
B).18c Recently, our group reported 4-acetamido-2,2,6,6,-
tetramethylpiperidine-N-oxyl (4-AcNH-TEMPO) catalyzed
we tested our previously reported conditions18b with
a
stoichiometric amount of 4-AcNH-TEMPO+BF4 . Gratifyingly,
-
the formation of octanenitrile was observed in 50% yield (entry
-
-
1). The use of TEMPO+BF4 instead of 4-AcNH-TEMPO+BF4
showed worse yield (entry 2). The oxidative nitriles synthesis
was carried out in different solvents such as CH3CN, CH2Cl2,
DMF, and DMSO, but none of them were superior to acetic acid
(entries 3–5).21 The use of other ammonium salts such as NH4Cl
and aqueous NH3 showed poor results (entries 6 and 7). The
acceptable yields were obtained when the reaction temperature
and the amount of ammonium salt were increased (entries 8–10).
-
The reduction of 4-AcNH-TEMPO+BF4 gave the octanenitrile
product in moderate yield (entry 11).
-
Table 2. Substrate scope of 4-AcNH-TEMPO+BF4 mediated
oxidative transformation of aliphatic aldehydes.a
Entry
1
Product
Yield (%) Entry
Product
Yield (%)
60
73
62
62
77
86
64b
8
Scheme 1. Previously reported oxoammonium salt-mediated
nitriles synthesis from aldehydes
2
3
4
5
6
9
67
94
53
63
65
10
11
12
13
aerobic oxidative conversions of aldehydes to nitriles using easily
accessible NH4OAc (Scheme 1, C).18b In this catalytic system,
various benzonitriles having electron-donating groups or
electron-withdrawing group were obtained in good yields,
however, the oxidative conversions of aliphatic aldehydes were
problematic. In the context of our interests in oxidation,20 we
envisioned that the use of stoichiometric amount of
oxoammonium salt with NH4OAc would provide a synthetic
route for the aliphatic nitriles synthesis.
Table 1. Optimization for oxoammonium salt-mediated
octanal to octanenitrile transformation.a
7
82
a Reaction conditions: aldehyde (0.3 mmol), 4-AcNH-TEMPO+BF4- (2.0
equiv), NH4OAc (4.0 equiv) in AcOH (0.6 mL) under N2 balloon at 70 oC for
12 h. b The yield was determined by GC
Entry
Oxoammonium salt
solvent
NH4X
(equiv)
Yield
(%)b
With the optimized conditions in hands (Table 1, entry 10),
the substrate scope of aliphatic aldehydes was investigated (Table
2). Both linear aldehydes including octanal, decanal, and 6-
chlorohexanal and branched aldehyde such as 2-ethylhexanal
showed good yields (entries 1–4). Interestingly, the aldehydes
which have no alpha proton exhibited better reactivity and
produced the corresponding nitriles in high yields (entries 5–7).
Although cyclohexanecarboxaldehyde and its derivatives showed
full conversions, the product yields were poor (entries 8 and 9).
The double bond in 3-cyclohexene-1-carboxaldehyde was
tolerable in the present oxidative nitrile synthesis (entry 10).
Hydrocinnamaldehyde derivatives were converted to the
corresponding nitriles albeit moderate yields (entries 11–13).
1
4-AcNH-TEMPO+BF4-
TEMPO+BF4-
AcOH
AcOH
CH3CN
CH2Cl2
DMF
NH4OAc (2.4)
NH4OAc (2.4)
NH4OAc (2.4)
NH4OAc (2.4)
NH4OAc (2.4)
NH4Cl (2.4)
50
38
40
20
33
13
38
48
60
73
47
2
3
4-AcNH-TEMPO+BF4-
4-AcNH-TEMPO+BF4-
4-AcNH-TEMPO+BF4-
4-AcNH-TEMPO+BF4-
4-AcNH-TEMPO+BF4-
4-AcNH-TEMPO+BF4-
4-AcNH-TEMPO+BF4-
4-AcNH-TEMPO+BF4-
4-AcNH-TEMPO+BF4-
4
5
6
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
7
NH3 (aq) (2.4)
NH4OAc (2.4)
NH4OAc (2.4)
NH4OAc (4.0)
NH4OAc (4.0)
8c
9d
10d
11d,e
The developed method was applied to the benzaldehydes for
the synthesis of benzonitriles (Table 3). Bezaldehydes which
have substituents at para position showed good reactivities
regardless of electronic environments (entries 1–7). Although 3-
methyl benzaldehyde showed a moderate yield (entry 8), the
oxidative transformation of 2-methyl benzaldehyde (entry 9) was
successful with high yield. Piperonylonitrile was synthesized by
the developed oxidative method with good yield and functional
a Reaction conditions: octanal (0.3 mmol), oxoammonium salt (2.0 equiv),
NH4X in solvent (0.6 mL) under N2 balloon at 50 oC for 12 h. b Yield
determined by 1H NMR spectroscopy (internal standard: 1,1,2,2-
tetrachloroethane). c at room temperature. d at 70 oC. e 1.0 equiv of
oxoammonium salt was used.

group tolerance (entry 10), however, the oxidative nitriles
synthesis of mesitaldehyde showed poor conversion and yield
presumably due to steric reason (entries 11). Not only vinyl
aldehyde such as cinnamaldehyde but also polyaromatic
aldehyde such as 1-naphthaldehyde underwent the developed
oxidative transformation smoothly (entries 12–13). In addition,
heteroaromatic nitrile was also synthesized (entry 14).
Interestingly, 1,3-dicyanobenzene was produced by the oxidation
of isophthalaldehyde (entry 15).22
to give the corresponding nitriles in good yields. The present
oxidative protocol was effective on large scale. The used
-
oxoammonium salt, 4-AcNH-TEMPO+BF4 , could be recycled by
the simple acid-base extraction and following oxidation with
HBF4, NaOCl, and NaBF4.
Acknowledgments
This work was supported by the Incheon National University
Research Grant in 2014.
-
Table 3. Substrate scope of 4-AcNH-TEMPO+BF4 mediated
oxidative transformation of benzaldehydes.a
Supplementary Material
Supplementary data (experimental procedures for oxidative
nitrile synthesis, and H and 13C NMR spectra of the products)
associated with this article can be found, in the online version, at
http://dx.doi.org/10.1016/j.tetlet.
1
Entry
1
Product
Yield(%) Entry
Product
Yield(%)
83
77
84
9
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a Reaction conditions: aldehyde (0.3 mmol), 4-AcNH-TEMPO+BF4- (2.0
equiv), NH4OAc (4.0 equiv) in AcOH (0.6 mL) under N2 balloon at 70 oC for
12 h.
The present oxidative nitriles synthesis was effective on larger
scale (Scheme 2). The exposure of 10 mmol of octanal to the
present reaction conditions provide octanenitrile in 71% yield. In
large scale, the use of stoichiometric amount of oxoammonium
salt was not plausible, however, the 4-AcNH-TEMPO radical
-
which is a reduced form of the used 4-AcNH-TEMPO+BF4 was
collected by simple acid-base extraction.23 The addition of HBF4,
-
NaOCl, and NaBF4 could regenerate 4-AcNH-TEMPO+BF4 for
recycle (50 %).24
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Scheme 2. Oxidative nitriles synthesis on larger scale.
In conclusion, we have developed oxoammonium salt-
mediated oxidative aldehydes to nitriles transformation with
readily accessible NH4OAc. Aliphatic aldehydes as well as
benzaldehydes underwent the developed oxidative transformation

4
Tetrahedron
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22. The yield was not increased even in the use of twice amount of
NH4OAc and 4-AcNH-TEMPO+BF4-. Further optimization was
not carried out.
23. The present reaction follows two electron oxidation mechanism.
During the oxidation of aldimine to nitrile, 4-AcNH-TEMPO+BF4-
was reduced into hydroxylamine (4-AcNH-TEMPOH). However,
the hydroxylamine and the remained 4-AcNH-TEMPO+BF4-
underwent comproportionation, then 4-AcNH-TEMPO radical
was generated. See ref 15b.
24. The purity of the regenerated 4-AcNH-TEMPO+BF4- was analyzed
by melting point and 1H NMR. See the supporting information for
details.

5
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Oxoammonium Salt-Mediated Oxidative
Nitriles Synthesis from Aldehydes with
Ammonium Acetate
Myeong Jin Kima, Junyoung Munb,*, Jinho Kima,*

6
Tetrahedron
Highlights
-
- A 4-AcNH-TEMPO+BF4 -mediated nitriles synthesis was achieved with ammonium acetate.
- Various aliphatic aldehydes as well as benzaldehydes underwent the present oxidation.
- The present protocol was effective on large scale.
-
- The used 4-AcNH-TEMPO+BF4 was recycled by extraction and the following oxidation.