Selective N-methylation of aliphatic amines with CO2 and hydrosilanes using nickel-phosphine catalysts

Article abstract of DOI:10.1021/om501176u

A method using CO₂ and PhSiH₃ for the methylation of primary and secondary aliphatic amines catalyzed by Ni (0) complexes was developed, selectively producing the monomethylated products in moderate to good yields. For that purpose, two catalysts were used: [(dippe)Ni(μ-H)]₂ and the commercially available Ni(COD)₂/dcype, both of which were rather efficient in this process. With a slight experimental modification, the reaction allowed the production of monomethylated ureas in good yields by using low amounts of PhSiH₃. On the basis of the experimental results, we propose a possible reaction mechanism for the formation of the new C-N bond.

Full text of DOI:10.1021/om501176u

Article
pubs.acs.org/Organometallics
Selective N‑Methylation of Aliphatic Amines with CO2 and
Hydrosilanes Using Nickel-Phosphine Catalysts
Lucero Gonzalez-Sebastian, Marcos Flores-Alamo, and Juventino J. García*
́
́
́ ́
Facultad de Química, Universidad Nacional Autonoma de Mexico, Mexico City 04510, Mexico
S
* Supporting Information
ABSTRACT: A method using CO2 and PhSiH3 for the
methylation of primary and secondary aliphatic amines
catalyzed by Ni (0) complexes was developed, selectively
producing the monomethylated products in moderate to good
yields. For that purpose, two catalysts were used: [(dippe)-
Ni(μ-H)]2 and the commercially available Ni(COD)2/dcype,
both of which were rather efficient in this process. With a
slight experimental modification, the reaction allowed the
production of monomethylated ureas in good yields by using
low amounts of PhSiH3. On the basis of the experimental
results, we propose a possible reaction mechanism for the formation of the new C−N bond.
the chemical industry, such as methyl-amines and urea
INTRODUCTION
■
derivatives. Methyl-substituted amines have been widely used
as key intermediates in the manufacture of pharmaceuticals,
agrochemicals, dyes, formulation agents, and polymers, or used
as solvents.12 The most common methodology for amine
methylation in industry uses toxic formaldehyde as the C1
source,13 whereas in laboratories, hazardous methylation
reagents like methyl iodide and dimethyl sulfate still prevail.14
Consequently, the application of safe and sustainable reagents
is highly desired. Considering this, during the past decade
dimethyl carbonate and methanol have been presented as
interesting “green” alternatives.14b,15 Very recently, Cantat,10l,16
Beller,17 and Leitner18 and co-workers reported that CO2 could
act as a methylating reagent with the use of Zn/NHC (Cantat)
or Ru/phosphine catalysts and hydrosilane or hydrogen gas as
reducing reagents (Beller and Leitner et al.). The 6-electron
reduction of CO2 with the formation of a N−C bond was
unknown until 2013, and only the above-mentioned catalytic
systems are currently known. Despite these great achievements,
the Ru/phosphine catalyst requires high CO2 pressures (30
bar)17b to carry out the methylation. Hence, research regarding
new, cheap, metal catalysts able to perform such a process
under milder conditions is still relevant. Herein, we disclose a
nickel/phosphine catalytic system able to perform the
monomethylation of primary and secondary aliphatic amines,
employing CO2 and hydrosilanes as methyl group sources.
The development of catalytic processes for the utilization of
carbon dioxide, a greenhouse gas, is of growing interest in
chemistry.1 Carbon dioxide is an abundant, nontoxic, nonflam-
mable, cheap, and renewable carbon source and therefore an
advantageous C1 building block. Various methodologies for
chemical transformation of CO2 to valuable chemicals have
been made to replace phosgene-based routes, by the catalytic
incorporation of CO2 into organic substrates for their
derivatization. One of the simplest reactions is the insertion
of CO2 (e.g., to obtain carbamates,2 carboxylate allyl derivates,3
acetic acid,4 dialkyl carbonates,5 polypyrones,6 lactones,7 and
polyurethanes).8 Nevertheless, the scope of organic molecules
directly produced from CO2 remains very strait, and only a
small number of commercial processes exist, such as the
production of urea (Bosch-Meiser process) and the synthesis of
cyclic carbonates, polycarbonates, and salicylic acid (Kolbe-
Schmitt synthesis).1c,9 Interestingly, these reactions result in the
functionalization of CO2 without a significant reduction of the
carbon oxidation state. Indeed, multielectron chemical
reduction of CO2 is indisputably the greatest difficulty facing
CO2 recycling, because highly active and inexpensive catalysts
are required to activate the stable CO2 molecule and promote
its reduction. With regard to this, recent important develop-
ments in the conversion of carbon dioxide into formates,
methanol (methoxides), and methane, using relatively mild
reducing agents (e.g., hydrosilanes, boranes, and H2) and a
suitable catalyst, have been reported.9c,f,10 Also of interest is the
design of efficient catalytic systems able to both reduce and
functionalize CO2 to form new bonds such as C−C, C−O, and
C−N, expanding the use of carbon dioxide as a C1-feedstock
for the production of fine chemicals.10k,l,11 In this context, the
C−N bond formation derived from CO2 and amines is of great
interest due to the importance of N-containing compounds in
RESULTS AND DISCUSSION
■
Following our interest in the reduction of CO2 with Et3SiH
catalyzed by the [(dippe)Ni(μ-H)]2 complex (A), we obtained
the reduction products of CO2, 3s and 4s, which can be
Received: November 21, 2014
© XXXX American Chemical Society
A
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Scheme 1. Reduction of CO2 Catalyzed by [(dippe)Ni(μ-H)]2
envisaged as intermediates in the CO2 reduction toward
methane formation (Scheme 1).19
temperature to 80 °C resulted in a low conversion of 1a in both
toluene and THF (entries 1 and 4, Table 1). Additionally, the
reaction time influences the conversion (entries 2 and 3).
Dibenzylurea (1e), N-benzylformamide (1f), and benzylisocya-
nate (1g) can be envisaged as intermediates in the catalytic
methylation of amines.
To increase the yield of N-methylbenzylamine (1b), we
decided to use higher amounts of PhSiH3 (4 and 6 equiv) but
otherwise use reaction conditions for entry 6 in Table 1
(Scheme 3).
As can be seen in Scheme 3, the use of higher amounts of
PhSiH3 in the methylation reaction of 1a increased the yield of
N-methylbenzylamine (1b). These preliminary results estab-
lished that the nickel complex (A) is an efficient catalyst for the
selective monomethylation of aliphatic amines; control experi-
ments under similar conditions but in the absence of (A) did
not produce any product.
Therefore, in order to improve the yields of 3s and 4s and
even complete the reduction of CO2 to methane, we decided to
assess the use of PhSiH3. However, we found that CO2 was
unreactive under a variety of reaction conditions; for example,
CO2 was unreactive using a mixture of PhSiH3 and [(dippe)-
Ni(μ-H)]2 (5% mol) at different temperatures (80 to 120 °C)
in a variety of solvents (THF, toluene, MeCN, and dioxane).
The improved version of the reaction in Scheme 1 is depicted
in Scheme 2, where Et3B was required to produce silyl formate
(Et3SiOCOH).19 Performing the reaction with PhSiH3 instead
of Et3SiH allowed the complete recovery of unreacted PhSiH3.
Scheme 2. Hydrosilylation of CO2 with Et3SiH Catalyzed by
[(dippe)Ni(μ-H)]2.19
Thus, we decided to extend the study to other nickel catalytic
systems for the methylation of amines using CO2 and PhSiH3.
We turned our attention to the Ni(COD)2/dcype (B) system,
and the main results for these experiments are summarized in
Table 2.
The results displayed in Table 2 show that commercially
available Ni(COD)2/dcype (B) is as good a catalyst as complex
(A) and therefore of more practical use. Having at hand both
active catalytic systems, we then assessed the scope of the
methylation of a variety of primary aliphatic amines, and
relevant results are in Tables 3 and 4.
The methylation reaction of aliphatic amines with 2 eq of
PhSiH3 using catalysts (A) and (B) (Table 3) yielded a
distribution of products with a reasonable selectivity toward the
corresponding N-methyl-N,N′-urea (product c); both catalysts
produced, in general, similar conversions. Surprisingly, aniline
exhibited low reactivity (Table 3, entry 7), which was
unexpected, considering previous reports where the authors
argued that the high reactivity of aromatic amines is because the
aromatic ring promotes the reduction of the corresponding
Therefore, due to the unexpected lack of reactivity for the
same systems using PhSiH3, we investigated the reaction of
carbon dioxide with benzylamine in the presence of PhSiH3 and
[(dippe)Ni(μ-H)]2 as a model system. The reaction was
assessed under different reaction conditions, and the results for
these experiments are summarized in Table 1.
All reactions were monitored by GC/MS, and the following
products were found: N-methylbenzyl-amine (1b), N-methyl-
N,N′-dibenzylurea (1c), N,N′-dibenzylformimidamide (1d),
N,N′-dibenzylurea (1e), N-benzylformamide (1f), and benzy-
lisocyanate (1g). The complete conversion of 1a was achieved
using toluene after 20 h at 100 °C, producing N-methyl-N,N′-
dibenzylurea (1c) in 80% yield (entry 6). In general, both
solvents were suitable for this reaction; however, toluene
provided the best conversions and selectivity toward the
methylated products (1b and 1c). Lowering the reaction
a
Table 1. Catalytic N-Methylation of Benzylamine with CO2 and PhSiH3
entry
solvent
T (oC)
t (h)
conv. of 1a (%)
1b (%)
1c (%)
1d (%)
1e (%)
1f (%)
1g (%)
1
2
3
4
5
6
THF
80
100
100
80
20
12
20
20
12
20
39
70
−
−
4
−
−
−
−
−
3
13
20
17
7
−
3
26
25
3
THF
22
69
38
61
80
THF
93
toluene
toluene
toluene
55
6
−
8
4
100
100
81
9
−
3
−
−
100
11
6
−
a
All reactions were carried out in a Schlenk flask equipped with a Rotaflo valve using 5 mL of solvent. Reaction conditions: mol ratio of 0.04:1:2 of
[(dippe)Ni(μ-H)]2, benzylamine, and PhSiH3, respectively, and 1 atm of CO2 were used. Conversions and yields were determined by GC/MS
analysis of the crude mixture.
B
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Scheme 3. N-Methylation of Benzylamine with CO2
a
Table 2. N-Methylation of Benzylamine Catalyzed with [(dippe)Ni(μ-H)]2 and [Ni(COD)2]/dcype
entry
catalyst
conv. of 1a (%)
eq of PhSiH3
1b (%)
1c (%)
1d (%)
1e (%)
b
c
1
2
3
4
[(dippe)Ni(μ-H)]2
100
100
100
100
2
4
2
4
11
66
6
80
22
82
27
6
3
9
3
9
3
[Ni(COD)2]/dcype
9
64
−
a
b
All reactions were carried out in a Schlenk flask equipped with a Rotaflo valve using 5 mL of solvent. Reaction conditions. Mol ratio of
c
0.01:0.25:0.5 or 1 of [(dippe)Ni(μ-H)]2, benzylamine, and PhSiH3, respectively, and 1 atm of CO2 were used. Mol ratio of 0.01:0.01:0.25:0.5 or 1
of [Ni(COD)2], dcype, benzylamine, and PhSiH3, respectively, and 1 atm of CO2 were used. Conversions and yields were determined by GC/MS
analysis of the crude mixture.
formamide.10l,17b,20 Hence, the lower reactivity of aniline can be
explained by the lower basicity of aromatic amines, compared
with aliphatic amines; this is included in the corresponding
mechanistic proposal depicted in Scheme 4 (vide infra).21
The results for the methylation reaction using 4 eq of PhSiH3
are displayed in Table 4. As a general trend, aliphatic amines
were methylated to yield the corresponding N-methylated
amine (b) in increased but moderate yields, along with three
other byproducts (products c, d, and e). Again, both catalysts
gave rather similar yields and product distribution. The use of
amines gave full conversion with the exception of aniline, entry
7. To note, the N,N-dimethylated amines were not detected in
any case (i. e., the current methodology allows selective
monomethylation of primary aliphatic amines).
product (b),10l and later, a condensation of b and 1 eq of
isocyanate gives the N-methyl-N′,N-urea (c). The isocyanate
(g) can be formed either by dehydration of carbamic acid or by
dehydrogenation of 2C. Isocyanate (g) may then react with 1
eq of amine to generate the corresponding urea (3C), followed
by reduction to yield d.
Finally, we assessed the reactivity of secondary aliphatic
amines under similar conditions; key results are in Table 5. The
use of dibenzylamine was rather informative, since reactivity
drops dramatically to yield only 42% of conversion at 150 °C in
toluene, with 35% yield of methy-dibenzylamine. The low
reactivity observed in secondary amines can be related to steric
factors and cancellation of pathways invoking isocyantes for
amine methylation.
Considering the results, we proposed a mechanism that
considers consecutive methylation of N−H bonds using CO2
and hydrosilanes, depicted in Scheme 4. The proposed
mechanism for the LnM-catalyzed process include the following
considerations: (i) even though it is a very well-known
process,9c,e,g,10j,m,n,19,22 the reduction of CO2 with PhSiH3 to
generate the corresponding silyl formate (R3SiOCOH) or
methoxysilane (R3SiOCH3) was not considered because CO2
was stable in the presence of PhSiH3 and the used nickel
catalysts. Moreover, both silyl formate and methoxysilane
species are electrophiles known to react with amines to yield
formamides and methylamines, respectively;23 (iii) the
formation of carbamic acid from amines and CO2 has been
documented;21,24 and (iv) the electrophile isocyanate is
considered a key reaction intermediate.24a,h
CONCLUSIONS
■
In summary, we have developed a general protocol for the
catalytic N-methylation of primary and secondary aliphatic
amines using CO2 as a C1 source and PhSiH3 as a reducing
agent, using nickel-based catalysts [(dippe)Ni(μ-H)]2 and the
commercially available Ni(COD)2/dcype. The monomethyla-
tion of aliphatic amines proceeds under relatively mild
conditions (atmospheric pressure of CO2), in moderate to
good yields. This methodology demonstrates for the first time
that nickel compounds are efficient catalysts in the selective N-
methylation of amines using CO2. The monomethylated ureas
were also obtained in good yields by using an appropriate
amount of PhSiH3. Finally, we proposed a possible mechanistic
reaction for these transformations, based on experimental
observations concerning the product distribution.
Considering the above, the initial step involves an oxidative
addition of PhSiH3 over Ni(0) to yield 1C followed by the
reaction with the carbamic acid generated in situ to produce the
formamide intermediate 2C along with silanol, then 2C is
further reduced to generate the corresponding methylated
EXPERIMENTAL SECTION
General Considerations. Unless otherwise noted, all operations
were carried out in a MBraun glovebox (<1 ppm of H2O and O2) or
■
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Table 3. Catalytic Methylation of Primary Aliphatic Amines Using CO2 and 2 eq of PhSiH3 Catalyzed by [(dippe)Ni(μ-H)]2 and
a
[Ni(COD)2]/dcype
a
b
All reactions were carried out in a Schlenk flask equipped with a Rotaflo valve using 5 mL of solvent. Reaction conditions. Mol ratio of
c
0.01:0.25:0.5 of [(dippe)Ni(μ-H)]2, benzylamine, and PhSiH3, respectively, and 1 atm of CO2 were used. Mol ratio of 0.01:0.01:0.25:0.5
[Ni(COD)2], dcype, benzylamine, and PhSiH3, respectively, and 1 atm of CO2 were used. Conversions and yields were determined by GC/MS
analysis of the crude mixture.
by using high-vacuum and standard Schlenk techniques under argon
atmosphere. Toluene was dried and distilled over sodium. Dioxane
and THF were dried and distilled from dark-purple solutions of
sodium/ketyl benzophenone. Deuterated solvents for NMR experi-
ments were purchased from Cambridge Isotope Laboratories and
stored over 3 Å molecular sieves in the glovebox. Compound
[(dippe)Ni(μ-H)]2 was prepared according to the reported
procedure.25 The bisphosphine ligand, dippe (1,2-bis-
diisopropylphosphino)ethane, was synthesized according to the
reported methods.26 [Ni(COD)2] (COD = 1,5-cyclooctadiene) and
dcype (1,2-bis-dicyclohexylphosphino)ethane were purchased from
Stream Chemical and stored in the glovebox. All other chemicals and
filter aids were reagent grade and were used as received. Carbon
dioxide was supplied by Air Products and Chemicals Inc. (purity >
99.99%) and used without further purification. All reagents for the
catalytic reactions were loaded in the glovebox using Schlenk flasks
equipped with Rotaflo high vacuum stopcocks and further loaded with
CO2. The crude reaction mixtures for each catalytic run were
immediately analyzed by GC/MS. GC/MS determinations were
performed using an Agilent 5975C system equipped with a 30 m DB-
5MS capillary (0.32 mm i.d.) column.
General Procedure for the Reaction of CO2, PhSiH3, and
[(dippe)Ni(μ-H)]2. A typical methodology was as follows: a 25 mL
Schlenk flask, equipped with Rotaflo valve and with an inner magnetic
stirring bar, was loaded into the glovebox with a solution of
[(dippe)Ni(μ-H)]2 (6.4 mg, 0.01 mmol) in THF (5 mL) and
PhSiH3 (108 mg, 1 mmol). A color change from wine red to brown
was immediately observed. The solution was stirred for 10 min, and
then a CO2 stream was bubbled at room temperature for 10 min. Then
the flask was closed and heated in an oil bath at 80 °C for 1 h. After
this time, the heating was stopped, and the flask was vented into the
hood. An aliquot of the reaction mixture was immediately analyzed by
GC/MS; only the unreacted PhSiH3 was observed. This methodology
was followed using toluene, dioxane, and acetonitrile instead of THF
at a variety of temperatures (80, 100, and 120 °C) and reaction times
(1 and 20 h), using 5 mol % of catalyst: [(dippe)Ni(μ-H)]2 (6.4 mg,
0.01 mmol) and PhSiH3 (22 mg, 0.2 mmol).
Reaction of CO2, PhSiH3, Et3B Catalyzed by [(dippe)Ni(μ-H)]2.
A 25 mL Schlenk flask equipped with a Rotaflo valve and a magnetic
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Table 4. Catalytic Methylation of Primary Aliphatic Amines Using CO2 and 4 eq of PhSiH3 Catalyzed by [(dippe)Ni(μ-H)]2 and
a
[Ni(COD)2]/dcype
a
b
All reactions were carried out in a Schlenk flask equipped with a Rotaflo valve using 5 mL of solvent. Reaction conditions. Mol ratio of 0.01:0.25:1
c
of [(dippe)Ni(μ-H)]2, benzylamine, and PhSiH3, respectively, and 1 atm of CO2 were used. Mol ratio of 0.01:0.01:0.25:1 [Ni(COD)2], dcype,
benzylamine, and PhSiH3, respectively, and 1 atm of CO2 were used. Conversions and yields were determined by GC/MS analysis of the crude
mixture.
stirrer was charged in the glovebox with a solution of [(dippe)Ni(μ-
H)]2 (6.4 mg, 0.01 mmol) in THF (5 mL), PhSiH3 (108 mg, 1 mmol),
and Et3B (9.8 mg, 0.1 mmol). A color change from wine red to brown
and effervescence were observed. The reaction mixture was stirred for
10 min, and then a CO2 stream was bubbled at room temperature for
10 min. After that, the flask was closed, followed by heating in an oil
bath at 80 °C for 1 h. Then, the flask was vented in a hood and
analyzed by GC/MS; unreacted PhSiH3 and traces of Ph2SiH2 and
Ph3SiH were observed. The very same procedure was followed using
toluene or dioxane instead of THF at different temperatures (80, 100,
and 120 °C) and times (1 and 20 h).
Typical Procedure for the N-Methylation of Amines
Catalyzed by [(dippe)Ni(μ-H)]2. A 25 mL Schlenk flask equipped
with a Rotaflo valve and a magnetic stirrer was charged in the glovebox
with a solution of [(dippe)Ni(μ-H)]2 (6.4 mg, 0.01 mmol) in toluene
(5 mL), amine (0.25 mmol), and PhSiH3 (108.2 mg, 1 mmol or 54.1
mg, 0.5 mmol). A color change from wine red to brown and
effervescence were observed. The reaction mixture was stirred for 10
min, and then a CO2 stream was bubbled at room temperature for 10
min. After that, the flask was closed followed by heating in an oil bath
at 100 °C for 20 h. After this time, the reaction mixture was cooled
down to room temperature, and the flask was vented in a hood,
exposed to air, and analyzed by GC/MS.
Typical Procedure for the N-Methylation of Amines
Catalyzed by [Ni(COD)2]/dcype. In a typical experiment, [Ni-
(COD)2] (2.8 mg, 0.01 mol) and dcype (4.3 mg, 0.01) were dissolved
in 5 mL of dry toluene in a 25 mL Schlenk flask equipped with a
Rotaflo valve and a magnetic stirrer and then amine (0.25 mmol) and
PhSiH3 (108.2 mg, 1 mmol or 54.1 mg, 0.5 mmol) were added, leading
to formation of a brown yellow solution. The reaction mixture was
stirred for 10 min. Then a CO2 stream was bubbled at room
temperature for 10 min. After that, the flask was closed and then
E
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Scheme 4. Mechanistic Proposal for the Methylation of Primary Aliphatic Amines by Nickel Complexes
a
Table 5. Catalytic Methylation of Secondary Aliphatic Amines Using CO2 and 4 eq of PhSiH3 Catalyzed by [Ni(COD)2]/dcype
entry
solvent
T (oC)
conv. of Ia′ (%)
Ib′ (%)
Ic′ (%)
1
2
3
THF
100
100
150
20
35
42
20
24
35
−
11
7
toluene
toluene
a
All reactions were carried out in a Schlenk flask equipped with a Rotaflo valve using 5 mL of solvent. Reaction conditions: mol ratio of
0.01:0.01:0.25:1 [Ni(COD)2], dcype, benzylamine, and PhSiH3, respectively, and 1 atm of CO2 were used. Conversions and yields were determined
by GC/MS analysis of the crude mixture.
heated in an oil bath at 100 °C for 20 h. After this time, the reaction
mixture was cooled down to room temperature, and the flask was
vented in a hood, exposed to air, and analyzed by GC/MS.
ACKNOWLEDGMENTS
■
We thank PAPIIT-DGAPA-UNAM (IN-210613) and CON-
ACYT (0178265 and Grant 271105) for their financial support
of this work. We also thank Dr. Alma Arevalo for her technical
assistance.
ASSOCIATED CONTENT
■
S
* Supporting Information
Selected GC/MS determinations and crystallographic data for
1,3-bis(4-fluorobenzyl)urea. This material is available free of
charge via the Internet at http://pubs.acs.org.
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Notes
The authors declare no competing financial interest.
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DOI: 10.1021/om501176u
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