Amines as effective ligands in iridium-catalyzed decarbonylative dehydration of biosourced substrates

Article abstract of DOI:10.1039/c8cy00621k

Linear α-olefins (LAOs) and linear internal olefins (LIOs) are essential intermediates in the synthesis of surfactants, lubricants, and polymers. Concurrently with petroleum-based industrial processes, the production of LAOs and LIOs from renewable feedstocks has gained increasing interest in recent years. Organometallic catalysts have been developed designedly, especially Pd, Fe and Ir catalysts. However, such catalysts are mostly stabilized by phosphanes, ligands sometimes difficult to handle especially on large scales. Alternatives to phosphanes would thus be highly desirable. In the present study, we demonstrate that Ir catalysts coordinated by amines are suitable to decarbonylate a wide range of biosourced substrates under mild conditions. The resulting LAOs and LIOs are obtained with good conversion provided that the nature and the quantity of the amines are controlled accurately. The LAO/LIO selectivity can also be tuned by a judicious choice of experimental conditions. Interestingly, the Ir-based catalytic system is applicable to the decarbonylative dehydration of saturated, unsaturated and polyunsaturated fatty acids.

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Amines as Effective Ligands in Iridium-Catalyzed Decarbonylative
Dehydration of Biosourced Substrates
Jérémy Ternel,a Bastien Léger,a Eric Monflier,a and Frédéric Hapiot*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Linear α-olefins (LAO) and linear internal olefins (LIO) are essential intermediates in the synthesis of surfactants,
lubricants, and polymers. Concurrently to petroleum-based industrial processes, the production of LAO and LIO from
renewable feedstocks has gained increasing interest in recent years. Organometallic catalysts have been developed
designedly, especially Pd, Fe and Ir catalysts. However, such catalysts are mostly stabilized by phosphanes, ligands
sometimes difficult to handle especially on large scales. Alternative to phosphanes would thus be highly desirable. In the
present study, we demonstrate that Ir catalysts coordinated by amines are suitable to decarbonylate a wide range of
biosourced substrates under mild conditions. The resulting LAO and LIO are obtained with good conversion provided that
the nature and the quantity of the amine are controlled accurately. The LAO/LIO selectivity can also be tuned by a
judicious choice of the experimental conditions. Interestingly, the Ir-based catalytic system is applicable to the
www.rsc.org/
decarbonylative
dehydration
of
satured,
unsaturated
and
polyunsatured
fatty
acids.
through coordinative chain-transfer polymerization.16 LIO are
mainly synthesized through LAO isomerization.17 To overcome
the dependence on petro-sourced products, environmentally
friendly processes should be developed. In this context, the
synthesis of LAO and LIO from renewable resources offers a
relevant alternative, both from an environmental and
economic point of view. Among renewables, unsaturated long-
chain aliphatic carboxylic acids, esters, and triglycerides are of
major interest. They constitute an eco-friendly alternative to
fossil feedstock as they are derived from vegetable oils and
animal fats.18 Several approaches have been developed to
functionalize these molecules by terminal or internal C=C
bond. One of them consists in the metathesis (especially
ethenolysis) of unsaturated vegetable oils and fatty acid
methyl esters (FAME).19,20,21,22,23,24,25,26,27,28,29 Another strategy
consists in fatty acids decarboxylation.30,31 Examples include
silica/alumina catalysts32 or Lewis-acid catalysts33 for the
selective production of LAO by decarboxylation of lactones and
unsaturated carboxylic acids. Decarbonylative dehydration of
fatty acid to give valuable odd-numbered LAO and LIO olefins
has also witnessed increasing interest.34 For example,
decarbonylation of heptanoic acid can be achieved over
carbon-supported Pt nanoparticles.35 However, turn-over
frequencies (TOF) are low because of catalyst
deactivation.36,37,38 A more recent strategy entails transition
metal-catalyzed decarbonylative dehydration of fatty acids. A
variety of metals have been shown to catalyze the
transformation such as Pd,39,40,41,42 Rh,43,44 Ni,45,46,47 Ir,48 and
Fe49 catalysts. Of interest, combination of Ir-catalyst, Ac2O and
KI allows for a decrease in the temperature reaction and an
increase in the product yield. We recently assessed the
catalytic performance of Ir catalysts coordinated by
Introduction
Linear
α-olefins (LAO) and linear internal olefins (LIO) have
become essential commodity chemicals with a global demand
surpassing millions metric tons. Both LAO and LIO can be
valorized separately. For example, LAO find application as co-
monomers for ethylene polymerization, and precursors to
plasticizers, lubricants and surfactants that are the basis for
shampoos, liquid hand soaps and dishwashing liquids.1 LIO, for
their part, are mainly used as synthetic-based drilling fluids
because they form more lubricious layers at the metal surface.
Their properties cause them to be used in paper sizing as well.
LAO and LIO can also be employed as mixtures containing
variable proportions of the two components. For example,
automotive manufacturers prefer to use synthetic lubricants
over conventional as they contain LIO. Their thermal stability
and lubricity help in preventing sludge formation in vehicle
engines, thus enhancing fuel efficiency, vehicle performance
and equipment life. Mixtures are also preferred in detergents
to increase their versatility.
From
a
synthesis viewpoint, the Fischer–Tropsch
process,2,3,4,5,6,7
and the oligomerization of
ethylene8,9,10,11,12,13,14 are the most developed processes to
synthesize short-chain LAO (C4–C8) while the Shell Higher
Olefin Process (SHOP) process leads to long-chain LAO and
LIO.15 A recent publication described the use of a trimetallic
catalyst system (Y–Al–Ni) for the tunable synthesis of LAO
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phosphanes in the decarbonylation of biosourced unsaturated excess NPh3 led to an encouraging 42% conversion within 8 h
fatty acids.50 The purity of the substrates, the nature of the Ir- and a rather balanced ratio between terminal and internal
coordinated phosphane, and the amounts of the additives (KI olefins (entry 3). Addition of KI greatly improved the catalytic
and Ac2O) are key parameters to optimize the catalytic activity as the conversion reached 88% and a higher selectivity
performance. There are, however, a number of problems that in terminal olefins (two thirds of the analyzed products). Note
are frequently encountered in the use of phosphane ligands. that TEM images recorded from the crude reaction solution
They are air-sensitive and the notorious degradation of P–C clearly showed the absence of Ir-nanoparticles under the
bonds can result in deactivation of the catalyst. To get rid of chosen catalytic conditions (ESI, Fig. S21). Changing NPh3 into
troublesome phosphanes, we recently envisaged the use of HNPh2, a considerably lower conversion was afforded (only
the more easy-to-handle amines as ligands. Herein, we 13% conv., entry 5), probably because of side-reaction of the
demonstrate that unsaturated biosourced fatty acids can be secondary amine with acetic anhydride that led to secondary
efficiently decarbonylated under relatively mild conditions amides whose coordination ability towards Ir complexes were
using Ir catalysts coordinated by amines under homogeneous lower than tertiary amines. Alkylamines also proved to be
catalytic conditions (Scheme 1). The studied phosphane-free effective in Ir-catalyzed decarbonylation of 1a (entries 6-13).
catalytic system is easy to implement as it proceeds under air However, none of them surpassed NPh3 whether in terms of
atmosphere. The conversion and LAO/LIO selectivity are catalytic activity or 2a/3a selectivity, irrespective of their class,
discussed throughout
a
detailed optimization of the and their electronic and steric properties. The best conversion
(72%) was measured with N,N,N′-TriMe-1,3-PD (entry 10) and
the best 2a/3a selectivity with N,N′-TetraMe-1,3-PD (entry 11).
Table 1. Ligand effect on conversion of 1a and 2a/3a
selectivity.a
Additive
(mol%)
Conv.b Sel.
experimental conditions. Interestingly, it is shown that the
LAO/LIO can be precisely tuned by a judicious choice of the
experimental conditions.
Entry
Ligand (mol%)
(%)
2a/
3ab
1
-
-
0
-
Scheme 1. Ir-catalyzed decarbonylative dehydration of unsaturated
fatty acids.
2
-
KI (50)
KI (50)
-
12
37
0
50/50
58/42
-
3c
2d
3
NPh3 (15)
NPh3 (15)
NPh3 (15)
NPh3 (15)
NHPh2 (15)
NEt3 (15)
EDe (15)
Results and discussion
Oleic acid (1a, 88 wt% purity), which contains only one carbon-
carbon double along its alkyl chain, was first chosen as a model
substrate to simplify the analysis of the reaction products.
[Ir(COD)Cl]2 (COD = cyclooctadiene) was considered as catalyst
precursor, and potassium iodide and acetic anhydride were
used as co-reactants (Table 1). Addition of KI causes ligand
exchange between Cl and I and exalts the reactivity of the Ir-
precursor.48 Acetic anhydride, for its part, condenses with oleic
acid to form a mixed anhydride. Oxidative addition of the
latter on the Ir-precursor gives the acyl iridium complex that
undergoes decarbonylation. We performed several catalytic
runs to examine the influence of various reaction conditions
on both activity and selectivity (Table 1; also see ESI, Table S1
for additional experiments). The formation of the
corresponding LAO (2a) and LIO (3a) was monitored by 1H
NMR spectroscopy (ESI). A blank catalytic test showed that no
reaction took place in the presence of [Ir(COD)Cl]2 without any
ligand and additive (Table 1, entry 1), even at higher
temperature (ESI, Table S1). Addition of KI led to a poor 12%
conversion (entry 2). Decarbonylation reactions were
performed under nitrogen. Under air atmosphere, a significant
decrease in the conversion was noticed probably because of
the formation of peroxides that inhibit the Ir-catalyst (entry 3).
Logically, if NPh3 (considered as the amino equivalent of PPh3)
was added in solution without metallic precursor, no
conversion could be detected. Combination of [Ir(COD)Cl]2 and
-
42
88
13
28
32
45/55
61/39
60/40
35/65
40/60
4
KI (50)
KI (50)
KI (50)
KI (50)
5
6
7
N,N,N′-TriMe-1,2-EDe
8
KI (50)
KI (50)
KI (50)
KI (50)
KI (50)
61
15
72
64
30
55/45
60/40
56/44
63/37
57/43
(15)
N,N-TetraMe-1,2-EDe
9
(15)
N,N,N′-TriMe-1,3-PDf
10
11
12
(15)
N,N′-TetraMe-1,3-PDf
(15)
Dicyclohexylamine
(15)
13
14
15
Dihexylamine (15)
DMF (15)
KI (50)
KI (50)
KI (50)
35
10
<5
45/55
59/41
-
pyridine (15)
4-dimethylamino-
pyridine (15)
16
KI (50)
0
-
aReaction conditions: Oleic acid 1a 88 wt% (1.0 mmol),
[Ir(COD)Cl]2 (0.025 mmol), acetic anhydride (2 mmol), 160 °C, 8
2 | J. Name., 2012, 00, 1-3
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h. bDetermined by 1H NMR spectroscopy. cunder air with PPh3 as a ligand.50 With 10 mol% NPh3, the conversion
atmosphere. dno iridium catalyst. eED = ethylenediamine. fPD = reached 48% and the products mixture consisted of two third
propylenediamine.
of 2a and one third of 3a (entry 2). The best conversion (78%)
was measured using 15 mol% NPh3, with little impact on the
Ligands featuring delocalized nitrogen such as DMF (entry 14) 2a/3a selectivity (entry 3). Further increase in NPh3 loading up
or aromatic amines such as pyridine (entries 15 and 16) gave to 30 mol% resulted in a drop in activity (entries 4 and 5). This
very low conversions. Their too weak -donating ability is not surprising as higher ligand to metal ratio may lead to the
σ
towards Ir probably prevented the formation of an effective Ir blocking of coordination sites, thereby reducing the catalytic
catalyst. Accordingly, NPh3 appears to be the best amine to activity.
stabilize Ir catalyst under such experimental conditions. NPh3 is
electronically and sterically suitable to provide a fine balance Table 2. Effect of ligand and precursor loading on conversion
3a selectivity.a
between (thermodynamic) stability and (catalytic) activity. In and 2a
/
Conv.b
(%)
<5
Sel.b
terms of catalytic activity, the Ir/NPh3 combination remained
Ligand
less efficient than the Ir/PPh3 couple (max. 78% conv. within
8h vs. 90% conv. within 5 h, respectively).50 The strong
coordinating PPh3 ligand promotes more stable and more
selective Ir catalysts, as anticipated by the HSAB concept.51 The
proportion of LIO is also higher using amines as ligands. While
Entry
(mol%)
2a/3a
-
1
2
3
4
5
NPh3 (5)
NPh3 (10)
NPh3 (15)
NPh3 (20)
NPh3 (30)
48
65/35
63/37
62/38
60/40
the 2a/3a ratio is up to 87/13 with the Ir-PPh3 catalyst, the
78
proportions of LIO can be as high as 65% with the Ir-NEt3
catalyst (entry 6). Note that, whatever the ligand, the extent of
isomerization was limited as only two isomerization products
(internal alkenes) could be detected by GLC (ESI, Fig. S19). Also
68
45
aReaction conditions: Oleic acid 1a 88 wt% (1.0 mmol),
[Ir(COD)Cl]2 (0.025 mmol), acetic anhydride (2 mmol), KI (0.5
mmol), 160 °C, 8 h.b Determined by 1H NMR spectroscopy.
Accordingly, most of the following catalytic experiments were
carried out using an optimal loading of 15 mol% amines.
note that a slight variation of the 2a/3a selectivity was
observed over time. For example, using N,N’-TetraMe-1,3-PD
as amine, it decreased from 69% after 2 h (18% conv.) to 56%
after 12 h (99% conv.) (ESI, Table S2).
The conversion and the 2a/3a selectivity could be optimized by
changing the ligand’s loading. No conversion was observed
using 5 mol% NPh3, suggesting that a minimum of ligands was
required to promote the formation of effective Ir-catalyst
(Table 2, entry 1). A similar trend had been found previously
Table 3. Effect of temperature on the catalytic performance.a
Ligand
Precursor
Temp
(°C)
120
140
160
180
180
180
120
140
160
180
180
180
Time
(h)
8
Conv.b
(%)
<5
2a/3a Sel.b
Entry
(mol%)
(mol%)
1
NPh3 (15)
[Ir(COD)Cl]2 (2.5)
[Ir(COD)Cl]2 (2.5)
[Ir(COD)Cl]2 (2.5)
[Ir(COD)Cl]2 (2.5)
[Ir(COD)Cl]2 (2.5)
[Ir(COD)Cl]2 (1)
[Ir(COD)Cl]2 (2.5)
[Ir(COD)Cl]2 (2.5)
[Ir(COD)Cl]2 (2.5)
[Ir(COD)Cl]2 (2.5)
[Ir(COD)Cl]2 (2.5)
[Ir(COD)Cl]2 (1)
-
2
NPh3 (15)
8
22
73/27
63/37
28/72
16/84
15/85
-
3
NPh3 (15)
8
78
4
NPh3 (15)
8
80
5
NPh3 (15)
16
16
8
100
89
6
NPh3 (10)
7
N,N′-TetraMe-1,3-PD (15)
N,N′-TetraMe-1,3-PD (15)
N,N′-TetraMe-1,3-PD (15)
N,N′-TetraMe-1,3-PD (15)
N,N′-TetraMe-1,3-PD (15)
N,N′-TetraMe-1,3-PD (10)
<5
8
8
20
66/34
64/36
26/74
5/95
6/94
9
8
64
10
11
12
8
78
16
16
100
82
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aReaction conditions: Oleic acid 1a 88 wt% (1.0 mmol), acetic anhydride (2 mmol), KI (0.5 mmol).b Determined by 1H NMR
spectroscopy.
Catalyst systems derived from NPh3 did show some sensitivity It was of interest to see if any difference could be observed in
to the reaction temperature. Less than 5% of 1a were Ir-catalyzed decarbonylation as function of the number and
converted at 120 °C within 8 h (Table 3, entry 1). Raising the location of the carbon-carbon double bonds along the chain of
temperature to 140 °C resulted in 22% conversion and a 2a/3a the carboxylic acids. To this end, we investigated the
selectivity of 73/27 (entry 2). Increasing the reaction decarbonylation of various biosourced substrates. Only oleic
temperature to 160 °C not only speeded up the conversion acid reacted to any appreciable extent, affording 99%
rate of 1a, but also promoted the formation of 3a (entry 3). conversion within 12 h at 160 °C (Table 4, entry 1). The Ir-
Further increase in the temperature up to 180 °C turned out to catalyst turned out to be slightly less active with the saturated
have a beneficial influence on the catalytic activity while the counterpart, namely stearic acid without affecting the LAO/LIO
selectivity was dramatically affected (2a
entry 4). Increasing the reaction time to 16 h allowed full decarbonylation of technical linolenic acid (47 wt% pure) in
conversion of 1a mainly into LIO (84%, entry 5). Reducing the terms of 2c 3c selectivity (entry 3). The presence of three
ligand loading to 10 mol% slightly altered the conversion and carbon-carbon double bonds did not disturb the selective
did not modify the 2a 3a selectivity (entry 6). Substituting pathway during the catalytic cycle as reflected in the constant
NPh3 by N,N′-TetraMe-1,3-PD did not change trends. The selectivity found for this system. However, a much reduced
effect on the 2a 3a selectivity was even amplified upon activity was observed as the conversion dropped to 66%. The
/3a ratio of 28/72, selectivity (entry 2). Little difference was seen in
/
/
/
increasing the temperature, as the proportion of isomerized drop in the catalytic activity was likely to be due to, among
products was greatly enhanced (entries 7-12). Note that N,N′- other reasons, the competitive coordination of unsaturations
TetraMe-1,3-PD led to the almost exclusive formation of LIO at to the Ir-catalyst, and hence low amount of active sites
180 °C. This is of great interest as pure LIO with a narrow accessible for catalysis. Compared to oleic acid, lengthening
carbon number range are usually produced in small quantities the alkyl chain caused significant decrease in both the
at a great cost. Whatever the amine, conversion and 2a/3a conversion and the selectivity. Thus, Ir-catalyzed
selectivity varied in opposite directions. Low conversion and decarbonylation of erucic acid afforded 86% conversion and a
large proportion of LAO were obtained at 140 °C while high 55/45
conversion and large amounts of LIO were measured at 180 °C.
selectivity
(entry
4).
Table 4. Ir-catalyzed decarbonylation of biosourced fatty acids.a
Entry
1
Substrate
Conversion (%)b
2a-f
/
3a-f Selectivityb
99
86
66
86
61/39
60/40
62/38
55/45
Oleic acid 88 wt% (1a
)
2
3
4
5
Stearic acid 98 wt% (1b
)
Linolenic acid 47 wt% (1c
)
Erucic acid 87 wt% (1d
)
55
72
55/45
53/47
10-undecenoic acid 98 wt% (1e
)
6c
Pripol 1012 (1f
)
aReaction conditions: 1a-1e (1.0 mmol), [Ir(COD)Cl]2 (0.025 mmol), NPh3 (0.15 mmol), acetic anhydride (2 mmol), KI (0.5
mmol), 160 °C, 12 h.b Determined by 1H NMR spectroscopy.c 1f (2.0 mmol), [Ir(COD)Cl]2 (0.050 mmol), NPh3 (0.30
4 | J. Name., 2012, 00, 1-3
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mmol), acetic anhydride (4 mmol), KI (1 mmol), 160 °C, 18 h.
The conversion was moderate for 10-undecenoic acid (only
55%, entry 5). As proposed for linolenic acid, the coordination
of the carbon-carbon double bond may be the cause of the
reduced catalytic activity. However, in that case, the effect was
not limited to the activity as the selectivity was also affected.
Actually, balanced proportions of LAO and LIO were obtained.
We were also interested in decarbonylating diacids of
industrial interest. Commercial Pripol 1012 (building block
manufactured by CRODA for coatings, adhesives and
engineering plastics) was efficiently decarbonylated producing
Notes and references
a
balanced 53/47 2f/3f ratio. The bifunctional LAO/LIO
products may especially find application in polymer chemistry.
Conclusions
1 G. J. S. Dawes, E. L. Scott, J. Le Nôtre, J. P. M. Sanders and J.
H. Bitter, Green Chem., 2015, 17, 3231-3250.
To summarize, the present investigation highlights the exciting
development of novel Ir-based catalytic systems combining
amines and iridium precursors to catalyze the decarbonylation
of a wide range of biosourced fatty acids, from satured to
polyunsatured derivatives. The catalytic system is readily
prepared in situ from commercially available and air stable
amine and iridium sources, circumventing the need for air-
sensitive organometallic complexes. Key parameters are the
nature and the amount of amines and the reaction
temperature. The reactivities demonstrated here undoubtedly
compete with those found for the most active systems that
have been recently developed, especially those based on
phosphanes. The main advantage of the studied process lies in
the tunability of the LAO/LIO selectivity of the Ir-catalyzed
decarbonylation reaction. Actually, the proportion of LAO and
LIO can be controlled by a relevant choice of the amine and
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3
M. E. Dry, in Fischer–Tropsch Technology (Eds.: A. P.
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10
dehydration almost exclusively to the formation of LIO. We
hope the present article will stimulate and guide future
empirical research on the synthesis of LAO and LIO, whether in
pure form or blended.
S. Kinoshita, K. Kawamura and T. Fujita, Chem. Asian J.,
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Acknowledgements
Wellenhofer and F. Mousa, Method for preparation of linear
alpha-olefins and reactor system therefore, WO No.
2008/086837A1, 2008.
This work was performed, in partnership with the SAS PIVERT,
within the frame of the French Institute for the Energy
Transition (Institut pour la Transition Energétique (ITE)
P.I.V.E.R.T.) (http://www.institut-pivert.com) selected as an
14 G. P. Belov, Catal. Ind., 2014, 6, 266-272.
Investment for the Future (“Investissements d’Avenir”). This 15 W. Keim, Angew. Chem. Int. Ed., 2013, 52, 12492-12496.
16
work was supported, as part of the Investments for the Future,
by the French Government under the reference ANR-001-01.
The TEM facility in Lille (France) is supported by the Conseil
Regional du Nord Pas de Calais and the European Regional
Development Fund (ERDF). We are grateful to Dr. M. Marinova
for his contribution in setting up the TEM measurements. We
thank CRODA France for the generous gift of Pripol 1012. We
also thank Dr. Nicolas Kania and D. Prevost for technical
assistance.
A. Gollwitzer, T. Dietel, W. P. Kretschmer and R. Kempe,
Nature Commun., 2017, 8, 1226.
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