Oxidative amination of benzylic alkanes with nitrobenzene derivatives as nitrogen sources

Article abstract of DOI:10.1016/j.tetlet.2016.11.057

The oxidative amination of inert C[sbnd]H bonds has the potential to fundamentally change chemistry but is severely limited by the low chemo- and regio-selectivity under oxidation conditions. Until now, no efficient methodology for the direct intermolecular amination of terminal sp³-C[sbnd]H bonds to N-alkyl amines has existed. Here, a new concept is proposed for the oxidative amination of the terminal sp³-C[sbnd]H bond in alkanes via the construction of a complex reaction system composed of a carbon-supported Co-Ni bimetallic catalyst, an alkane, nitrobenzene, tert-butyl hydroperoxide and hydrogen. This system allows the reduction of nitrobenzene to aniline and the further oxidative amination of the alkane. Nitrobenzene and toluene derivatives can be successfully transformed into the corresponding N-benzyl aniline derivatives with up to 95% isolated yields, and the reaction shows excellent functional group tolerance. This approach offers a new concept for catalyst design and may strongly promote the study of inert C[sbnd]H bond activation and the synthesis of functional N-containing compounds.

Full text of DOI:10.1016/j.tetlet.2016.11.057

Accepted Manuscript
Oxidative Amination of Benzylic Alkanes with Nitrobenzene Derivatives as
Nitrogen Sources
Shaofeng Pang, Feng Shi
PII:
S0040-4039(16)31525-8
DOI:
http://dx.doi.org/10.1016/j.tetlet.2016.11.057
TETL 48343
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
14 October 2016
11 November 2016
14 November 2016
Please cite this article as: Pang, S., Shi, F., Oxidative Amination of Benzylic Alkanes with Nitrobenzene Derivatives
as Nitrogen Sources, Tetrahedron Letters (2016), doi: http://dx.doi.org/10.1016/j.tetlet.2016.11.057
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1
Tetrahedron Letters
Oxidative Amination of Benzylic Alkanes with Nitrobenzene Derivatives as
Nitrogen Sources
Shaofeng Pang†‡ and Feng Shi*†
†State Key Laboratory for Oxo Synthesis and Selective Oxidation, Center for Green Chemistry and Catalysis, Lanzhou Institute of Chemical Physics, Chinese
Academy of Sciences, No. 18, Tianshui Middle Road, Lanzhou, China.
‡University of Chinese Academy of Sciences, Beijing, 100049
Supporting Information Placeholder
ARTICLE INFO
ABSTRACT
The oxidative amination of inert C-H bonds has the potential to fundamentally change chemistry
but is severely limited by the low chemo- and regio-selectivity under oxidation conditions. Until
now, no efficient methodology for the direct intermolecular amination of terminal sp3-C-H
bonds to N-alkyl amines has existed. Here, a new concept is proposed for the oxidative
amination of the terminal sp3-C-H bond in alkanes via the construction of a complex reaction
system composed of a carbon-supported Co-Ni bimetallic catalyst, an alkane, nitrobenzene, tert-
butyl hydroperoxide and hydrogen. This system allows the reduction of nitrobenzene to aniline
and the further oxidative amination of the alkane. Nitrobenzene and toluene derivatives can be
successfully transformed into the corresponding N-benzyl aniline derivatives with up to 95%
isolated yields, and the reaction shows excellent functional group tolerance. This approach
offers a new concept for catalyst design and may strongly promote the study of inert C-H bond
activation and the synthesis of functional N-containing compounds.
Article history:
Received
Received in revised form
Accepted
Available online
Keywords:
oxidative amination
C-H bond
sp3-C-H
N-alkyl amine
2009 Elsevier Ltd. All rights reserved.
a. Corresponding author: fshi@licp.cas.cn; Fax: +86 931 8277088; Tel: +86 931
Introduction
4968142
Alkanes are the most plentiful organic bases that are easily
accessible. Almost all chemical intermediates or products, i.e., fuels,
solvents, pharmaceuticals and new materials, are generated via
multi-step transformations of alkanes1. Among these transformations,
the selective functionalization of the sp3-C-H bond is a major
challenge 2-6. In fact, to date, the sole perfect catalyst system for
methane activation is the specific enzyme found in nature, which has
been elucidated and mimicked by chemists for a long time7. Over the
last decades, rapid progress has been made, and excellent results
have been obtained in this field.
catalyzed by Mn-,24 Ag-25, Rh-26, Ru-27, Co-28 and Cu-29based
catalysts has been demonstrated. Oxidative C-N bond formation
between a carboxamide and an alkane over Pd30-32 Ag33, Co34, Ni35,
and Cu36,37, as well as under metal-free conditions, has been
developed38,39. C-N bond formation reactions occurred with nitrogen
sources containing active groups such as –N340,41, PhI=42, and –OH43.
Good results were obtained in the α-amination of aldehydes and
secondary sp-3-C tertiary carbons; in addition, the cyclization
reaction promoted C-H activation of aliphatic amines for strained
nitrogen heterocycle synthesis44-47. However, only a few results were
reported for the direct reaction between the terminal sp3-C-H and an
amine to form N-alkyl amine, and no general methodology exists for
the one-pot synthesis of N-benzyl aniline with aniline/nitrobenzene
and toluene as the starting materials (Scheme 1). This reaction would
result in severe tar formation because of aniline oxidation as well as
resulting in imine generation because the N-benzyl aniline is easily
oxidized. Herein, we report the one-pot amination of the primary sp-
3-C-H bond in terminal alkanes with nitrobenzene as the nitrogen
source in the presence of a suitable amount of hydrogen, which could
restrain the aniline oxidation because it was released slowly and
reacted soon after its formation.
In the field of fine chemicals, a classical route for alkane
conversion to nitrogen compounds is through chemical synthesis.
Generally, multi-step chemical reactions were used, and a large
amount of byproducts were produced if the reaction was initiated
from the halogenation or oxidation of the alkane molecule to an alkyl
halide, alcohol or aldehyde, followed by aminations with amines to
generate N-alkyl amines8. Over the last years, numerous approaches
for the direct amination of alcohols have been demonstrated, either
via nucleophilic substitution or via the borrowing hydrogen reaction
mechanism. Typically, metal triflates/halides could promote
nucleophilic substitution pathways in the amination of allylic
alcohols9, whereas transition-metal, carbon and enzyme catalysts
were used in the borrowing hydrogen reaction mechanism10-22
.
Undoubtedly, the one-pot amination of alkanes is highly desirable
both in academic and industrial fields. In fact, extensive efforts have
been made for the aminations of alkanes with specific N-containing
molecules. 23 The oxidative amination of alkanes and sulfonamides
Scheme 1. Oxidative amination of benzylic alkanes with
nitrobenzene derivatives as nitrogen sources.

2
Tetrahedron
TBHP and 4 MPa H2 (Table 1, Entries 11-13). It should be
mentioned that this catalyst can be easily recovered and recycled,
and 93% yield was maintained when it was used in the 3rd run
(Table 1, Entry 14). As control reactions, the activity of Ni2O3,
Co3O4 and Ni2O3/Co3O4 were tested under the same reaction
conditions (Table 1, Entries 14-16), and the yields of N-benzyl
aniline were 24-27%. Thus Ni2O3, Co3O4 or Ni2O3/Co3O4 mixture
can not be used as active catalyst directly.
Results and Discussion
Our investigation starts with the oxidative amination of toluene with
aniline as the nitrogen source and tert-butyl hydroperoxide (TBHP)
as the oxidant.
Table 1. Catalyst screening and reaction conditions optimizationa
To reveal the structure of the active Co-Ni/C catalyst, it was
extensively characterized using X-ray diffraction (XRD), X-ray
photoelectron spectroscopy (XPS), N2-adsorption desorption and
transmission electron spectroscopy (TEM). Typically, the cobalt and
nickel loadings were approximately 6 wt% (catalyst samples were
determined using inductively coupled plasma atomic emission
spectroscopy (ICP-AES)), and the BET surface areas ranged from
200-500 m2/g (Fig. S1). XRD characterization of the catalysts
suggested that almost all metals inside the catalysts were amorphous
and that no diffraction pattern could be observed for the nickel-,
cobalt-, copper- and iron-based materials (Fig. S2). The XPS spectra
of the catalysts showed that with the exception of the copper species,
none of the other metals could be observed, indicating that these
metals might be trapped inside the nano-pores of the carbon supports
(Fig. S3). Based on the Cu2p3/2 XPS spectra, metallic copper might
form in Cu/C. Interestingly, the XPS spectra of Co2p3/2 and Ni2p3/2
were observed after the Co-Ni/C catalyst was used for 3 runs. These
results suggested the formation of Ni2O3 and Co3O4, and it is
possible that the real surface structure of Co-Ni/C during the reaction
consists of these oxides.
Entry
Catalyst
Co/C
Conversion /%b
Yield/%b
32
1
2
3
4
5
6
7
8
9
60
93
57
90
99
96
94
95
99
Ni/C
50
Cu/C
36
Fe/C
20
94[c]
Co-Ni/C
Cu-Ni/C
Fe-Ni/C
Co-Ni/C-Cel
58
49
83
81
Co-Ni/XC-
72R
10
Co-Ni/C[d]
Co-Ni/C[e]
Co-Ni/C[f]
Co-Ni/C[f]
Co-Ni/C
Co3O4
93
92
99
99
99
62
82
11
77
12
95[c]
95[c]
93
12
13[g]
14[h]
27
15[h]
16[h]
Ni2O3
54
53
24
27
Co3O4/Ni2O3
a0.5 mmol nitrobenzene, 10 mL toluene, 60 mg catalyst, 5.5 mmol
b
TBHP, 5.0 MPa H2, 160 OC, 36 h. Determined by GC-FID using
c
d
biphenyl as the external standard material. Isolated yield. 2 mmol
e
f
TBHP was used. 1 MPa H2 was used. 40 mg catalyst, 4 mmol
TBHP, 4.0 MPa H2. The catalyst was recovered and used at the 3rd
g
run. Entries 1-7 and 10-13, Carbon source = lignin. Entry 8, Carbon
source=cellulose, and were denoted as C-Cel. hThe same metal
loadings as those in 40 mg Co-Ni/C catalyst.
First, a series of carbon-supported transition metal catalysts with
lignin as the carbon source was tested with the oxidative amination
of toluene as the model reaction. Moderate yields of N-benzyl aniline
were obtained (Table 1, Entries 1-4). However, an interesting
phenomenon was observed when we checked the results, revealing
that a better mass balance was achieved when Ni/C was used as the
catalyst; this finding is in agreement with our previous results that Ni
is a potential species for nitrobenzene reduction and the alcohol
amination reaction18,48. In addition, it has been shown that Co(Ⅱ) or
Co(Ⅲ) is a good choice for the oxidation of alkanes to alcohols49.
These results inspire us because they suggest that we can construct a
complex catalyst system by combining Ni and Co into a single
system for the reductive-oxidative amination of toluene with
nitrobenzene. To our delight, an excellent result was achieved when
the Co-Ni/C catalyst was prepared and tested. The isolated yield of
N-benzyl aniline reached 94% (Table 1, Entry 5). For the other
bimetallic catalysts, such as Cu-Ni/C and Fe-Ni/C, only moderate
yields were obtained (Table 1, Entries 6-7). Relatively good results
were also obtained when Co and Ni were supported on activated
carbon (XC-72R) or with cellulose as the carbon source (Table 1,
Entries 8-9). Note that the carbonization ratio of lignin was ~50%,
while it was only ~14% when cellulose was used. Therefore, the
synthesis will be more valuable with lignin as the carbon source for
the preparation of the catalyst. Then, the reaction conditions were
further optimized, and 95% isolated yield was achieved with 4 mmol
Figure 1. TEM, HR-TEM and STEM images of Co-Ni/C before
(left) and after use (right)
Next, the TEM characterizations showed that the particle sizes of
Co and Ni species were ~10-15 nm (Fig. 1 and Fig. S4). Additionally,
coagulation of the Co and Ni particles occurred during the reaction.
The HR-TEM images suggest that a Co-Ni alloy may form, but it is
difficult to define the Ni and Co species because their lattice
distances are close to each other. Then, the STEM characterization
confirmed the formation of a Co-Ni alloy that might be responsible

3
for the high activity of the Co-Ni bimetallic catalyst for the oxidative
amination of toluene derivatives.
nitro-3-(trifluoromethyl)pyridine
and
1-chloro-4-
(methylsulfonyl) -2-nitrobenzene gave 73-90% yields (c25-c27).
Note that the α-amination of cyclic olefins can progress smoothly
without any reduction of the double bonds, and the yields of c28-
c30 reached 90%. In addition, the presence of thioether, an easily
oxidizable group, is also tolerated in the reaction. Compounds
c31 and c32 can be synthesized with 68% and 70% yields,
respectively. The amination of toluene and cyclopentene can
progress well with nitrobenzene derivatives containing
sulfonamide and amide groups, and up to 90% yields were
obtained. Note that no reaction occurred on the sulfonamide and
amide groups.
Then, the scope and generality of this catalyst in the amination of
toluene derivatives were explored (Scheme 2). First, the aminations
of toluene with nitrobenzene derivatives were examined. Typically,
the yield of N-benzyl aniline was 94% (c1). The steric effect can be
observed when p-, o- or m-Me nitrobenzene was used as the starting
material. The yields of their corresponding products were 93%, 87%
and 50% (c2-c4). When 2,6-di-Me nitrobenzene was used as the
starting material, only 31% yield of the desired product was obtained
(c5). Good to excellent results were also obtained if nitrobenzene
derivatives with other substituting groups, such as -Cl, MeO-, Ph-,
MeSO2-, Naphth-, and F3C-, were used as the starting materials. The
yields of the desired products ranged from 70-94% (c6-c16). The
amination of other alkanes can also be performed. For example, N-
(1-phenylethyl) aniline can be synthesized with 64% yield via the
reaction of ethyl benzene with nitrobenzene (c17). The amination of
ethyl benzene was also realized with p-Ph-nitrobenzene as the
nitrogen source, and 81% yield of the desired product was obtained
(c18).
Scheme 3. Results of oxidative amination of benzylic alkanes with
nitrobenzene derivatives containing different functional groups. The
reaction conditions are the same as those in the footnote of Scheme 1.
Finally, isotope tracing reactions were performed to examine the
possible reaction mechanism of the amination reactions with
nitrobenzene and d8-toluene as the model substrates. Based on the
ion selective spectra of the benzyl group of the final product
molecules, it can be observed that only d7-benzyl aniline was
obtained at the initial stage of the reaction when it was reacted for 50
min (Scheme 4a and Fig. S5-a). When the reaction was prolonged to
36 h, which was the same length as that used in the normal reactions,
15% (determined by ion selective MS) or 14% deuterium
Scheme 2. Results of oxidative amination of toluene derivatives with
nitrobenzene derivatives. 0.5 mmol nitrobenzene derivatives, 10 mL
alkane, 40 mg catalyst, 4.0 mmol TBHP, 4.0 MPa H2, 160 OC, 36 h.
Isolated yields.
Since this reaction system requires the presence of both an
oxidant and a reducing agent, it would be highly interesting to
explore whether the reaction tolerates the presence of reducible
and oxidizable functional groups (Scheme 3) such as carbonyl,
olefin, nitrile, thioether, amide and sulfonamide groups because
these groups are important moieties in bio-active molecules50.
Carbonyl is easily observable in many functional molecules;
therefore, nitrobenzene derivatives with aldehyde or ketone
groups were first examined. To our delight, 87% and 80%
isolated yields of compounds c19 and c20 were obtained,
respectively. The yields of c21-c23, for which the ketone groups
were at different positions of the aromatic rings of the
nitrobenzene derivatives, were 70-87% via the aminations of
toluene, o-Cl-toluene and ethyl benzene. Therefore, our catalyst
system is suitable for the amination of toluene with nitrobenzene
derivatives containing aldehyde or ketone groups. Furthermore,
the presence of a nitrile group does not influence the reactivity of
nitrobenzene, and a 67% yield of c24 was obtained. The presence
of a carbonyl group in the aromatic ring of toluene is also
applicable in the amination reactions. The amination reactions of
methyl 3-methylbenzoate with p-Ph-nitrobenzene, 2-chloro-5-
1
(determined by H NMR) of the –CD2- in the benzylic group was
replaced by hydrogen in the final product (Schemes 4b and 4c and
Fig. S5-b). This finding should be attributed to the reversibility of the
entire reaction (Scheme 4d). The aldehyde is also not the possible
intermediate. If aldehyde was the reaction intermediate, then the
reaction would take the reductive amination pathway, and at least
50% of the hydrogen atoms would be observed in the benzylic group.
In order to clarify the reaction intermediate, the reaction was traced
by GC-MS, and the formation of benzyl alcohol and benzaldehyde
were observed. Therefore, benzyl alcohol and benzaldehyde were
used as the starting materials under the same reaction conditions but
only 10% and 13% yields to N-benzyl aniline were obtained. These
results suggested they were not the possible reaction intermediates.
So the real reaction intermediate is still not clear at this stage.
Conclusion
In conclusion, the intermolecular amination of terminal sp3-C-H
bonds was realized for the first time with excellent yields via the
reduction of nitrobenzene to aniline and the further oxidative

4
Tetrahedron
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http://www.sciencedirect.com.XXX
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Graphical Abstract
Oxidative Amination of Benzylic Alkanes
with Nitrobenzene Derivatives as Nitrogen
Sources
Leave this area blank for abstract info.
Shaofeng Pangand Feng Shi

5
Highlights




Intermolecular amination of sp3-C-H bonds with nitrobenzene was realized.
Excellent reducible and oxidizable functional groups toleration.
Isotope tracing reacions revealed oxidative amination mechanism.
Co-Ni alloy nano-particle might be the active catalyst species.