From Internal Olefins to Linear Amines: Ruthenium-Catalyzed Domino Water-Gas Shift/Hydroaminomethylation Sequence

Article abstract of DOI:10.1021/acscatal.5b02457

A selective ruthenium-catalyzed water-gas shift/hydroformylation of internal olefins and olefin mixtures is reported. This novel domino reaction takes place through a catalytic water-gas shift reaction, subsequent olefin isomerization, followed by hydrofo

Full text of DOI:10.1021/acscatal.5b02457

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Article
From Internal Olefins to Linear Amines: Ruthenium-catalyzed
Domino Water-gas Shift/Hydroaminomethylation Sequence
Jie Liu, Christoph Kubis, Robert Franke, Ralf Jackstell, and Matthias Beller
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.5b02457 • Publication Date (Web): 22 Dec 2015
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ACS Catalysis
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From Internal Olefins to Linear Amines: Ruthenium-Catalyzed
Domino Water-Gas Shift/Hydroaminomethylation Sequence
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Jie Liu,† Christoph Kubis,† Robert Franke,‡,§ Ralf Jackstell,† and Matthias Beller*†
†Leibniz-Institut für Katalyse e.V., an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany
‡Evonik Industries AG, Paul-Baumann-Str. 1, 45772 Marl, Germany
§Lehrstuhl für Theoretische Chemie, 44780 Bochum, Germany
ABSTRACT: A selective ruthenium-catalyzed water-gas shift/hydroformylation of internal olefins and olefin mixtures is
reported. This novel domino reaction takes place through a catalytic water-gas shift reaction, subsequent olefin isomeri-
zation, followed by hydroformylation and reductive amination. Key to the success for the efficient one-pot process is the
use of a specific 2-phosphino-substituted imidazole ligand and triruthenium dodecacarbonyl as pre-catalyst. Industrially
important internal olefins react with various amines to give the corresponding tertiary amines generally in good yield and
selectivity. This reaction sequence constitutes an economically attractive and environmentally favorable process for the
synthesis of linear amines.
KEYWORDS: internal olefin, linear amine, ruthenium, water-gas shift, hydroaminomethylation, domino reaction.
[M]
INTRODUCTION
CO
+
H2O
CO2
+
H2
O
(1)
(2)
Aliphatic amines are produced as valuable intermediates
in the bulk and fine chemical industries.1 They are used as
agrochemicals, pharmaceutical intermediates, solvents,
dyes, monomers for polymerization and functional mate-
rials.2 Nowadays, methods such as reductive amination of
carbonyl compounds,3 amination of alcohols,4 and hydro-
genation of the respective nitriles,5 prevail in industry. In
addition, a plethora of less atom-efficient methodologies
such as classical nucleophilic substitution of alkyl
halides3a and cross coupling reactions,6 or less general
methods like hydroamination of alkenes,3a, 7 are continu-
ously being investigated for laboratory scale synthesis.
Despite all these known processes, there is still consider-
able interest to develop improved routes to this class of
compounds. An environmentally benign synthesis of
amines from olefins is the so-called hydroaminomethyla-
tion reaction.8 This domino sequence includes hydro-
formylation of olefins to aldehydes, followed by conden-
sation with amine to imines or enamines and final hydro-
genation gives the desired alkylated amines (Scheme 1, (2)
to (4)). A number of protocols for hydroaminomethyla-
tion of terminal olefins have been disclosed in recent
years,9 however, more challenging is the synthesis of line-
ar amines from internal olefins. Such reactions are of
industrial relevance because mixtures of internal olefins
such as butenes, hexenes and octenes are more cost-
efficient than the corresponding terminal olefins. Thus,
our group developed the first general catalyst system for
linear amine synthesis from internal olefins in 2002
(Scheme 2, Eq. 1).10 This work was inspired by related
hydroformylations of internal olefins to give linear prod-
ucts.11
[M]
R2
+
CO/H2
R1
H
R1
R2
O
condensation
R1
NR3R4
+ H2O
HNR3R4
+
(3)
(4)
R1
H
R2
R2
R1
imine or enamine
[M]
NR3R4
R1
NR3R4
+
H2
R2
R2
Scheme 1. Domino water-gas shift / hydroaminomethyla-
tion sequence. (1) Metal catalyzed water gas shift reaction.
(2) Hydroformylation of olefins. (3) Condensation of al-
dehyde and amine. (4) Hydrogenation of imine or
enamine.
Interestingly, most of the known hydroformylation re-
actions of internal olefins require relatively expensive
rhodium/ligand catalyst systems to ensure high activity
and selectivity in the carbonylation step.12 Hence, it is
highly desirable to apply less costly alternative metals to
realize this process.13 In this regard, it is noteworthy that
recently the groups of Nozaki,14 Krische,15 Ding,16 Acker-
mann17, Sanford18 and others19 as well as ourselves20 have
reported ruthenium-catalyzed C-C and C-hetero bond
formation reactions and demonstrated their potential and
application to hydroformylation reactions. Moreover, in
1970s, homogeneous ruthenium,21 as well as rhodium22
and platinum23 catalysts were found to demonstrate good
activity for water gas shift reaction (Scheme 1, (1)), then
these catalytic systems were further applied to hydro-
fomylation and hydrogenation reactions.24 In this context,
our group firstly presented hydrogen-free ruthenium-
catalyzed hydroaminomethylation of terminal olefins in
2014 (Scheme 2, Eq. 2).25 Although high yields and regi-
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oselectivities were obtained with terminal olefins, unfor- methoxyphenyl)-1H-imidazole) as the most efficient lig-
1
2
3
4
5
6
7
8
tunately, internal olefins showed only low activity in this
reaction. These results intrigued us to develop a more
general, practical and complementary ruthenium-
catalyzed hydroaminomethylation of industrial im-
portantly internal olefins.
and afforded 3a in 95% yield and good regioselectivity (n/i
= 87:13). Notably, L3 with a less basic phenyl substituent
on the phosphorus suppressed this reaction. L4 bearing
i
the Pr group on phosphorus also provided good regiose-
lectivity albeit gave slightly lower yield. Other imidazole
ligands, such as L5 and L6, displayed high yields, while
with moderate regioselectivities were observed. Benzim-
idazole-type ligand L6 did not present any improvement
in this reaction. Changing the imidazolyl moiety to pyrrol,
pyrazol, and aromatic type ligands (L8-L10), the catalytic
performance was declined. These results demonstrate
that a hemilabile behaviour27 between the imine nitrogen
of the imidazolyl unit and the ruthenium center may play
an important role in this catalytic transformation.28
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Scheme 2. Hydroaminomethylation of olefins for the
synthesis of linear amines. Eq. 1, rhodium catalyzed hy-
droaminomethylation of internal olefins. Eq. 2, ruthenium
catalyzed water-gas shift/hydroaminomethylation of
terminal olefins.
In order to produce linear amines from internal olefins
via hydroaminomethylation, a suitable catalytic system
should fulfil several requirements: (1) This domino se-
quence consists of water-gas shift reaction, olefin isomer-
ization, hydroformylation, condensation and final hydro-
genation (Scheme 1) and the catalyst system should be
compatible with all these steps; (2) to selectively produce
linear amines, the hydroformylation of the terminal olefin
must occur much faster and with high regioselectivity
compared with the reaction of the internal olefin; (3) the
catalyst must be active, selective for the hydrogenation
step of imine or enamine under CO pressure.
Based on our continuing interest in hydroformylation
using so-called “alternative metal” catalysts, recently we
showed the catalytic activity of ruthenium catalysts in the
presence of 2-phosphino-substituted imidazole ligands in
Figure 1. Ligand effects for the water-gas shift / hydroam-
inomethylation sequence of 2-octene with piperidine.
Reaction conditions: 1a (1.3 mmol), 2a (1.0 mmol),
Ru3(CO)12 (0.5 mol%), monodentate ligand (1.5 mol%),
bidentate ligand (0.75 mol%), Na2CO3 (5.0 mol%), CO (40
bar), THF (1.5 mL), H2O (0.1 mL), 140 oC, 20 h. Yields and
selectivity were determined by GC analysis using isooc-
tane as the internal standard.
hydroformylation
reactions.26 These results inspired us to apply such cata-
lytic systems for the selective water-gas
and
hydroaminomethylation
shift/hydroaminomethylation of internal olefins.
RESULTS AND DISCUSSION
At the start of this project, we evaluated the effect of
different ligands using 2-octene 1a and piperidine 2a as
model substrates (Figure 1). In the absence of any ligand,
only 13% yield of the desired 1-nonyl piperidine 3a was
obtained with a low regioselectivity. Using PPh3 or PCy3
as ligands did not improve the activity or selectivity.
Then, we investigated the effects of other reaction pa-
rameters for the benchmark reaction, and the results are
summarized in Table 1. When Ru3(CO)12 was replaced by
Fe3(CO)12, essentially no reaction occurred (entry 2). Con-
trol experiments showed that the ruthenium catalyst and
water are essential for this reaction (entries 3 and 4).
Decreasing the temperature to 120°C led to significantly
slower conversion, affording only 9% yield of 3a (entry 5).
As to the solvent, toluene also gave good regioselectivity
albeit lower yield was obtained (entry 6), while dipolar
aprotic NMP showed less efficiency in terms of chemical
yield (entry 7). Notably, the reaction without base
However,
in
the
presence
of
L1
(2-
(dicyclohexylphosphanyl)-1-phenyl-1H-imidazole) a high
yield of 3a (93%) and good regioselectivity (n/i = 86:14)
was observed. To elaborate the influence of this ligand
structure on the catalyst reactivity, more heterocyclic and
aromatic phosphine ligands were employed (L2 to L10). To
our delight, applying L2 (2-(dicyclohexylphosphanyl)-1-(2-
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demonstrated lower yield, but still significant activity
(entry 8). Addition of benzoic acid instead of Na2CO3 led
to no improvement for this transformation (entry 9).
Table 2. Variation of different internal olefins for the
synthesis of amines.a
1
2
3
4
5
6
Table 1. Domino water-gas shift/hydroaminomethylation
of 2-octene 1a with piperidine 2a: Effects of reaction pa-
rameters. a
7
8
Major product
Yield
[%]
Entry
Olefin
n:i
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
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1
94
85
87:13
89:11
80:20
65:35
91:9
-
2
3
4
5
6
Entry
Variation from "Standard Condition"
None
Yield [%]
n:i
87:13
-
72b
22 b
77
1
95
0
2
3
4
5
6
7
8
9
Fe3(CO)12 instead of Ru3(CO)12
Without Ru3(CO)12
0
-
Without water
0
-
120 oC instead of 140 o
C
9
87:13
87:13
85:15
87:13
87:13
85
Toluene instead of THF
NMP instead of THF
Without Na2CO3
65
33
71
73
7
78
-
3f1:3f2
87:13
Benzoic acid instead of Na2CO3
8
9
81
71
53
a
Standard reaction conditions:
mmol), Ru3(CO)12 (0.5 mol%), L2 (1.5 mol%), Na2CO3 (5.0
mol%), CO (40 bar), THF (1.5 mL), H2O (0.1 mL), 140 C,
20 h. Yield and selectivity were determined by GC analy-
sis.
1a (1.3 mmol), 2a (1.0
3g1:3g2
59:41
o
3h1:3h2:
3h3
10
With the optimized reaction conditions in hand, we
explored the substrate scope. At first, the reactions of
various internal olefins 1 with piperidine 2a were studied.
We were pleased to find that related internal olefins (2-
hexene, 3-hexene) reacted well to give the corresponding
linear amines in good yield and regioselectivity (Table 2,
entries 1-3). On the other hand, 4-octene gave only 22%
yield with moderate regioselectivity (Table 2, entry 4).
Functionalized 4-hexen-1-ol also reacted smoothly with a
good yield (77%) and high regioselectivity (n:i = 91:9)
(Table 2, entry 5). Interestingly, cyclic olefins including
cyclohexene, norbornene, and indene were found to be
suitable substrates to afford the corresponding amines in
high yields (Table 2, entries 6-8). 2,3-Dihydrofuran, which
represents an enol ether substrate, provided a good yield
but poor regioselectivity (Table 2, entry 9). With (1E)-1-
propenylbenzene, a mixture of three different amines was
obtained (Table 2, entry 10). When limonene and (−)-β-
citronellene were used as the substrates, the internal
bond remained intact and only the double bond in the
terminal positions were selectively hydroformylated to
the corresponding amines with moderate to good results
(Table 2, entries 11-12).
34:8:58
11
58
90
99:1
99:1
12
a
Reaction conditions:
Ru3(CO)12 (0.5 mol%), L2 (1.5 mol%), Na2CO3 (5.0 mol%),
CO (40 bar), THF (1.5 mL), H2O (0.1 mL), 140 C, 20 h.
Isolated yield. Selectivity was determined by GC analysis.
1 (1.3 mmol), 2a (1.0 mmol), Ru3(CO)12 (1.0 mol%), L2 (3.0
mol%), Na2CO3 (5.0 mol%), CO (40 bar), THF (1.5 mL),
H2O (0.1 mL), 140 C, 20 h. Yield and selectivity was de-
termined by GC analysis.
1 (1.3 mmol), 2a (1.0 mmol),
o
b
o
Furthermore, the reactivity of different amines was in-
vestigated using 2-octene as substrate (Table 3). With
cyclic secondary amines like morpholine and 1-
phenylpiperazine, good yields and regioselectivities were
achieved (Table 3, entries 1 and 2). Acyclic amines such as
di-n-butylamine, and (2-methylamino)ethanol also un-
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derwent this transformation smoothly in moderate and
high yields and regioselectivities (Table 3, entries 3 and
4). Secondary benzylic amines were found to be suitable
substrates, too; however product yields were only moder-
ate (Table 3, entries 5-6). Finally, indoline was alkylated
under the reaction conditions, albeit in low yield (Table 3,
entry 7).
mmol), Ru3(CO)12 (0.5 mol%), L2 (1.5 mol%), Na2CO3 (5.0
mol%), CO (40 bar), THF (1.5 mL), H2O (0.1 mL), 140 C,
20 h. Isolated yield. Selectivity was determined by GC
analysis.
o
1
2
3
4
5
6
7
8
Next, we were interested in demonstrating the utility of
this method for the hydroaminomethylation of industrial-
ly important building blocks (Scheme 3). Here, crack C4,
a mixture including 1-butene, 2-butenes, isobutene and
butanes, which is a product from cracking of naphtha
(light gasoline), reacted to the corresponding linear
amines 3s and 3s’ in high yield and regioselectivity with
only 0.2 mol% Ru3(CO)12 . Additionally, a mixture of oc-
tenes, which is mainly manufactured by oligomerization
of ethylene, was also applied to this reaction and gave 81%
yield of 3a with a selectivity of n:i=81:19.
Table 3. Substrates scope for different amines. a
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Entry
1
Amine
Major product
Yield [%]
65
n:i
nC5H11
N
3k
85:15
O
Finally, the reaction progress of this ruthenium-
catalyzed water-gas shift/hydroformylation of 2-octene 1a
and piperidine 2a was examined in more detail. As de-
picted in Figure 2a, the gas consumption started only
after 2.5 hours and within this time only small amounts of
E/Z isomerization of 2-octene were observed. Then, 2-
octene 1a was consumed slowly and at the same time, the
corresponding amine 3a and other internal octenes (3-
octene and 4-octene) were formed (Figure 2b). It is note-
worthy that 1-octene, which is proposed as the intermedi-
ate in this transformation, was not accumulated during
the reaction. In agreement with our previous work,26a, 26b
this result is attributed to the faster hydroformylation of
terminal olefins. In addition, neither aldehyde, enamine
nor imine were detected during the whole reaction time,
which illustrates a fast process of the aldehyde with the
amine and subsequent hydrogenation reaction.
2
65
84:16
3
4
5
87
77
63
86:14
75:25
84:16
6
7
35
18
85:15
86:164
a
Reaction conditions:
1a (1.3 mmol), 2 (1.0 mmol),
(a)
o
Ru3(CO)12 (0.5 mol%), L2 (1.5 mol%), Na2CO3 (5.0 mol%),
Temp.
160
(
C
)
∆P bar
20
o
temp.
∆P bar
CO (40 bar), THF (1.5 mL), H2O (0.1 mL), 140 C, 20 h.
140
120
100
80
Isolated yield. Selectivity was determined by GC analysis.
15
10
5
60
40
20
0
0
5
10
15
20
25
Time (hour)
(b)
%
2ꢀoctene
1ꢀoctene
octane
100
other octene
amine
80
60
40
20
0
Scheme 3. Synthetic applications by using crack C4 and a
mixture of octenes. Reaction conditions: For crack C4
(0.72 g), 2a (10 mmol), Ru3(CO)12 (0.2 mol%), L2 (0.6
mol%), Na2CO3 (5.0 mol%), CO (50 bar), THF (15 mL),
o
0
5
10
15
20
25
H2O (1 mL), 140 C, 72 h. Isolated yield. Selectivity was
Time (hour)
determined by GC analysis. For octenes (1.3 mmol), 2a (1.0
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344, 1037-1057; (c) Bini, L.; Müller, C.; Wilting, J.; von
Figure 2. (a) Δp (Pressure change compared to initial
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Etienne, S., J. Am. Chem. Soc. 2010, 132, 7854-7855; (g)
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2014, 5, 4111.
pressure) curve and temperature curve. (b) Composition
of the reaction mixture.
CONCLUSIONS
In summary, we have developed a novel domino se-
quence for the conversion of internal olefins to linear
amines via catalytic water-gas shift reaction, subsequent
olefin isomerization, followed by hydroformylation and
reductive amination. Comparing with expensive rhodium
catalyst, as a less costly alternative metal, ruthenium also
demonstrates good reactivity and selectivity in this reac-
tion. More importantly, in the presence of a special imid-
azole ligand, the corresponding linear amines are ob-
tained in general in moderate to good yields and regios-
lectivity. Interestingly, the conversion of industrially
available bulk mixtures of olefins such as crack C4 and
octenes proceed in excellent yields considering the num-
ber of reaction steps. This procedure is expected to com-
plement the current methods for hydroaminomethylation
reactions in organic synthesis.
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AUTHOR INFORMATION
Corresponding Author
*E-mail: matthias.beller@catalysis.de
Notes
The authors declare no competing financial interest.
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2010, 49, 2626-2629; (j) Liu, G.; Huang, K.; Cai, C.; Cao, B.;
Chang, M.; Wu, W.; Zhang, X., Chem.–Eur. J. 2011, 17, 14559-
14563; (k) Crozet, D.; Gual, A.; McKay, D.; Dinoi, C.; Godard, C.;
Urrutigoïty, M.; Daran, J.-C.; Maron, L.; Claver, C.; Kalck, P.,
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R.; Beller, M., Chem. Commun. 2015, 51, 5059-5062.
ACKNOWLEDGMENT
We are particularly grateful to the Bundesministerium für
Bildung und Forschung (BMBF) for financial support under
the PROFORMING project (BMBF-03X3559) and Evonik
Industries AG for providing the industrial raw materials: C4
mixture and octene mixture. J. Liu thanks the Chinese Schol-
arship Council for financial support. We thank the analytical
department of Leibniz-Institute for Catalysis at the Universi-
ty of Rostock for their excellent analytical service here.
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