Catalytic decarbonylation of biosourced substrates

Article abstract of DOI:10.1002/cssc.201500214

Linear α-olefins (LAO) are one of the main targets in the field of surfactants, lubricants, and polymers. With the depletion of petroleum resources, the production of LAO from renewable feedstocks has gained increasing interest in recent years. In the present study, we demonstrated that Ir catalysts were suitable to decarbonylate a wide range of biosourced substrates under rather mild conditions (160 °C, 5 h reaction time) in the presence of potassium iodide and acetic anhydride. The resulting LAO were obtained with good conversion and selectivity provided that the purity of the substrate, the nature of the ligand, and the amounts of the additives were controlled accurately. The catalytic system could be recovered efficiently by using a Kugelrohr distillation apparatus and recycled.

Full text of DOI:10.1002/cssc.201500214

DOI: 10.1002/cssc.201500214
Full Papers
Catalytic Decarbonylation of Biosourced Substrates
Jꢀrꢀmy Ternel,[a] Thomas Lebarbꢀ,[b] Eric Monflier,[a] and Frꢀdꢀric Hapiot*[a]
Linear a-olefins (LAO) are one of the main targets in the field
of surfactants, lubricants, and polymers. With the depletion of
petroleum resources, the production of LAO from renewable
feedstocks has gained increasing interest in recent years. In
the present study, we demonstrated that Ir catalysts were suit-
able to decarbonylate a wide range of biosourced substrates
under rather mild conditions (1608C, 5 h reaction time) in the
presence of potassium iodide and acetic anhydride. The result-
ing LAO were obtained with good conversion and selectivity
provided that the purity of the substrate, the nature of the
ligand, and the amounts of the additives were controlled accu-
rately. The catalytic system could be recovered efficiently by
using a Kugelrohr distillation apparatus and recycled.
Introduction
Linear a-olefins (LAO) are extremely important chemical feed-
stocks for industrial and consumer products. Although long-
chain LAO (C10–C14) play an important role in the production of
surfactants and lubricants, short-chain LAO (C4–C8) are used in
substantial amounts as co-monomers in the production of
high-density polyethylene (HDPE) and linear low-density poly-
ethylene (LLDPE). The two main commercial processes to
obtain LAO are the oligomerization of ethylene[1–6] and the
Fischer–Tropsch process starting from syngas.[7–11] However,
these present some drawbacks such as lower yields of long-
chain LAO (C10–C14) compared to short-chain LAO (C4–C8) cou-
pled with a decrease in selectivity because of the formation of
branched olefins and isomerization reactions. The production
of LAO with an odd number of carbon atoms appears to be
impossible by ethylene oligomerization.
nolysis, the triglyceride of a-decenoic acid is the copro-
duct.[20–25] Although these coproducts are interesting bi- or tri-
functional molecules with potentially valuable applications, the
overall yield of a-olefins is low, for example, only 43% w/w of
glycerol trioleate is converted into the desired high-value LAO.
Similarly, metathesis has been used widely to cleave fatty acid
derivatives to lead to unsaturated long-chain a-olefins.[26] How-
ever, numerous byproducts were formed concomitantly, which
thus limits the interest of such an approach. Other strategies
were also developed to produce long-chain olefins by one
carbon degradation. Among them, fatty acids decarboxylation
has been investigated extensively.[27] Recent examples demon-
strated the use of Lewis-acid catalysts for the selective produc-
tion of LAO by the decarboxylation of lactones and unsaturat-
ed carboxylic acids[28] and described the combination of a P450
fatty acid decarboxylase with a light-driven, in situ H2O2 gener-
ation system for the selective and quantitative conversion of
fatty acids into terminal alkenes.[29] Concurrently, fatty acid de-
carbonylation has gained increasing interest recently. For ex-
ample, the decarbonylation of heptanoic acid over carbon-sup-
ported Pt nanoparticles was reported,[30] but low turn-over fre-
quencies (TOF) were measured because of catalyst deactiva-
tion.[31–33] Better results were obtained using homogeneous
catalysts.[34–39] The Pd-catalyzed decarbonylative dehydration of
fatty acids was performed using a low loading of Pd catalyst
stabilized by the Xantphos ligands and proceeded under sol-
vent-free conditions.[40,41] Ir and Fe catalysts were also effective
to decarbonylate saturated fatty acids.[42] On using Ir catalysts,
the addition of Ac2O and KI allowed the reaction temperature
to be decreased and improved the product yield. KI caused
ligand exchange between Cl and I, and Ac2O helped to gener-
ate an acid anhydride in situ that subsequently underwent oxi-
dative addition onto the Ir catalyst. The resulting acyl iridium
complex consecutively underwent decarbonylation to afford
the alkyl iridium complex and b-hydride elimination to give
a terminal alkene.
Recently, it was shown that LAO can be produced from re-
newable resources as a means to address environmental and
economic concerns. Among them, unsaturated long-chain ali-
phatic carboxylic acids, esters, and triglycerides are of major in-
terest as they can be derived from abundant feedstocks such
as vegetable oils and animal fats. As such, they constitute an
eco-friendly alternative to fossil feedstocks. The introduction of
a terminal C=C bond within these molecules has been envis-
aged using several approaches. The first method consisted of
the ethenolysis of unsaturated vegetable oils and fatty acid
methyl esters (FAME).[12–19] A major drawback of this approach
is that besides the expected product, a coproduct is formed in
a 1:1 ratio. For example, in the case of glycerol trioleate ethe-
[a] Dr. J. Ternel, Prof. Dr. E. Monflier, Prof. F. Hapiot
Unitꢀ de Catalyse et de Chimie du Solide—UCCS Artois
University of Artois
Facultꢀ Jean Perrin, SP18, 62307 Lens Cedex (France)
E-mail: frederic.hapiot@univ-artois.fr
[b] Dr. T. Lebarbꢀ
ITERG
11 rue Monge, Parc Industriel Bersol 2, 33600 Pessac (France)
Except for the oxidative decarboxylation of unsaturated fatty
acids,[43] it appears that many of the catalytic systems studied
Supporting Information for this article is available on the WWW under
http://dx.doi.org/10.1002/cssc.201500214.
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addition of excess PPh3 im-
proved the conversion (91%;
Table 2, entry 18). A 3:1 mixture
of PPh3/[Ir(COD)Cl]2 was consid-
ered as it was one of the best
catalytic systems. The catalytic
conditions were further opti-
mized by varying the amount of
Scheme 1. Ir-catalyzed decarbonylation of unsaturated fatty acids.
the additives (Table 3). Conver-
sions were very low in the ab-
so far have focused on saturated fatty acid substrates. In this
context, we assessed the catalytic performance of Ir catalysts
in the decarbonylation of biosourced unsaturated fatty acids
(Scheme 1).
sence of acetic anhydride (Table 3, entry 1) or potassium iodide
(Table 3, entry 2). An increased amount of KI led to an increase
in both the conversion and the terminal alkene selectivity
(Table 3, entries 3 and 4).
Herein, we demonstrate that a wide range of unsaturated bi-
osourced fatty acids could be decarbonylated efficiently under
relatively mild conditions using Ir catalysts under homogene-
ous catalytic conditions. The conversion and selectivi-
ty in terminal olefins are discussed throughout a de-
However, a slight increase of the amount of KI produced no
effect on the catalytic performance (Table 3, entry 8). A de-
crease of the quantity of acetic anhydride impacted the con-
tailed optimization of the experimental conditions.
Table 1. Selectivity of the Ir-catalyzed decarbonylation reaction for saturated and un-
saturated derivatives.[a]
Entry Substrate
Ligand[b] Precursor[b]
[mol%] [mol%]
Conversion[c] 2/3 selectivi-
[%]
Results and Discussion
ty[c]
To begin with, oleic acid (99 wt% purity) was chosen
as a model substrate. The presence of only one C=C
bond on the alkyl chain simplified the analysis of the
reaction products greatly. To evaluate the impact of
the unsaturation on the catalytic performance, a com-
parison with stearic acid was performed using IrCl(-
CO)(PPh3)2 and [Ir(COD)Cl]2 (COD=cyclooctadiene) as
Ir catalysts and potassium iodide and acetic anhy-
dride as co-reactants (Table 1).[44] The reaction prod-
1
2
3
4
stearic acid 98%
(1a)
oleic acid 99% (1b)
–
–
IrCl(CO)(PPh3)2
(5)
IrCl(CO)(PPh3)2
(5)
[Ir(COD)Cl]2 (2.5) 86
80
95:5
84
89:11
95:5
91:9
stearic acid 98%
(1a)
oleic acid 99% (1b) PPh3
PPh3
(15)
[Ir(COD)Cl]2 (2.5) 95
(15)
[a] Reaction conditions: 1.0 mmol substrate, 2 mmol acetic anhydride, 0.5 mmol KI,
1608C, 5 h. [b] Molar percentage with respect to the substrate. [c] Determined by
1H NMR spectroscopy and confirmed by GC.
1
ucts were monitored and analyzed by H NMR spec-
troscopy (Supporting Information). At 1608C, the de-
carbonylation of oleic acid within 5 h led to higher
conversions compared to stearic acid but to lower se-
Table 2. Effect of the ligand and the metallic precursor on the selectivity
of the Ir-catalyzed decarbonylation reaction.[a]
lectivity in terminal alkenes (Table 1). Accordingly, the presence
of the C=C bond did not affect the catalytic performance sig-
nificantly.
Entry Ligand[b]
[mol%]
Precursor[b]
[mol%]
Conversion[c] 2/3 selectivity[c]
[%]
The amount and the nature of the ligand was then varied
(Table 2). If [Ir(COD)Cl]2 was used as the catalyst, a very small
conversion could be measured in the absence of any ligand
(<5%, Table 2, entry 1). An increase of the amount of Ir cata-
lyst and PPh3 favored both the conversion and selectivity
greatly, and the best result was obtained for a PPh3/[Ir(COD)Cl]2
ratio of 3 (Table 2, entry 5) with a 5 mol% of Ir catalyst with re-
spect to the substrate. The substitution of the aromatic rings
of PPh3 in the para position by Cl, F, or tBu had a deleterious
effect on the conversion (Table 2, entries 7, 8, and 9). Substitu-
tion in the para and meta positions by a methyl group showed
no change (Table 2, entries 10 and 11), whereas substitution in
the ortho position deactivated the catalyst (Table 2, entries 12
and 13). Bidentate ligands such as 1,4-bis(diphenylphosphino)-
butane (dppb), Xantphos, and bis-[2-(diphenylphosphino)phe-
nyl]ether (DPE-phos) were ineffective (Table 2, entries 14, 15,
and 16). If IrCl(CO)(PPh3)2 was used as the catalyst, similar con-
version and selectivity were obtained (Table 2, entry 17). The
1
2
3
4
5
6
7
8
–
[Ir(COD)Cl]2 (2.5) <5
–
PPh3 (5)
[Ir(COD)Cl]2 (0.5)
[Ir(COD)Cl]2 (1)
39
68
92
90
89
34
56
75
89
86
77:23
84:16
84:16
87:13
86:14
78:22
84:16
84:16
85:15
85:15
–
PPh3 (10)
PPh3 (10)
PPh3 (15)
PPh3 (20)
p-Cl-PPh3 (15)
p-F-PPh3 (15)
p-tBu-PPh3 (15) [Ir(COD)Cl]2 (2.5)
p-tolyl-PPh3 (15) [Ir(COD)Cl]2 (2.5)
m-tolyl-PPh3 (15) [Ir(COD)Cl]2 (2.5)
o-tolyl-PPh3 (15) [Ir(COD)Cl]2 (2.5) <5
o-OMe-PPh3 (15) [Ir(COD)Cl]2 (2.5) <5
dppb (10)
Xantphos (10)
DPE-phos (10)
–
[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)
9
10
11
12
13
14
15
16
17
18
–
–
–
–
[Ir(COD)Cl]2 (2.5) <5
[Ir(COD)Cl]2 (2.5) <5
[Ir(COD)Cl]2 (2.5) <5
IrCl(CO)(PPh3)2 (5) 84
IrCl(CO)(PPh3)2 (5) 91
85:15
87:13
PPh3 (10)
[a] Reaction conditions: 1.0 mmol oleic acid 88% (1b’), 2 mmol acetic an-
hydride, 0.5 mmol KI, 1608C, 5 h. [b] Molar percentage with respect to
the substrate. [c] Determined by H NMR spectroscopy.
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5), very low conversions were obtained. Attempts were also
made in aqueous biphasic conditions using sulfonated ligands
to retain the Ir catalyst in water.
Table 3. Effect of acetic anhydride and additive on the Ir-catalyzed decar-
bonylation reaction.[a]
Entry
Anhydride
[mmol]
Additive[b]
[mol%]
Conversion[c]
[%]
2/3 selectivity[c]
Very low conversions were obtained if the benchmark
3,3’,3’’-phosphanetriyltris(benzenesulfonic acid) trisodium salt
(TPPTS) or the more organophilic p-(tris-Me)-TPPTS [sodium
5,5’,5’’-phosphinetriyltris(2-methylbenzene sulfonate)] and p-
(tBu)-TPPDS sodium (3,3’-{[4-(tert-butyl)phenyl]phosphinediyl}-
dibenzene sulfonate) were used even in the presence of a sur-
factant such as cetyl trimethylammonium bromide (CTAB;
Table 4, entry 6).
1
2
3
4
5
6
7
8
–
KI (50)
–
0
<5
78
90
46
85
94
89
–
–
Ac2O (2)
Ac2O (2)
Ac2O (2)
Ac2O (1)
Ac2O (1.5)
Ac2O (3)
Ac2O (2)
KI (20)
KI (50)
KI (50)
KI (50)
KI (50)
KI (100)
83:17
87:13
82:18
85:15
86:14
87:13
[a] Reaction conditions: 1.0 mmol oleic acid 88% (1b’), [Ir(COD)Cl]2
(2.5 mol%), PPh3 (15 mol%), 1608C, 5 h. [b] Molar percentage with re-
spect to the substrate. [c] Determined by 1H NMR spectroscopy and con-
firmed by GC.
Table 5. Effect of various metallic precursors on the decarbonylation re-
action.[a]
Entry
Precursor
Conversion[b]
[%]
2/3 selectivity[b]
version significantly by a factor of two (Table 3, entry 5);
whereas a higher proportion of acetic anhydride gave a higher
conversion (Table 3, entry 7). The best compromise to access
high conversion and selectivity was obtained using 2 equiva-
lents of Ac2O and 0.5 equivalents of KI with respect to the sub-
strate (Table 3, entry 4). Aliquots of acetic anhydride were
added every half hour to the reaction mixture (1, 0.5, 0.3, and
0.2 mmol, respectively) to optimize the conversion as de-
scribed by Stoltz et al.[41] However, no significant variation in
the conversion could be noticed whatever the amount of
acetic anhydride (Supporting Information). Catalytic reactions
without Ac2O were performed (Table 4), and harsh experimen-
tal conditions were required. With IrCl(CO)(PPh3)2 as the cata-
1
[Ir(COD)Cl]2 (2.5)
IrCl(CO)(PPh3)2 (5)
PdCl2 (5)
Rh(acac)CO2 (5)
Rh(acac)CO2 (5)
RhCl3 (5)
90
91
0
77
99
0
87:13
87:13
–
59:41
51:49
–
2[c]
3
4
5[d]
6
[a] Reaction conditions: 1.0 mmol oleic acid 88% (1b’), PPh3 (15 mol%),
KI (50 mol%), 1608C, 5 h. [b] Determined by 1H NMR spectroscopy.
[c] PPh3 (10 mol%). [d] KI (100 mol%).
To assess the catalytic performance of Ir catalysts, other met-
allic precursors were also tested (Table 5). Although PdCl2 and
RhCl3 did not show any catalytic activity, Rh(acac)CO2
(acac=acetylacetonate) was rather effective, especial-
ly with excess KI (Table 5, entry 5). However, the se-
lectivity in terminal alkenes was very low compared
Table 4. Ir-catalyzed decarbonylation reaction performed without Ac2O.[a]
Entry Precursor[b]
[mol%]
Ligand[b]
[mol%]
T
Conversion[c] 2/3 selectivity[c]
to that of Ir catalysts.
[8C] [%]
The effect of the substrate purity on the catalytic
performance was also investigated (Table 6). A de-
crease of the purity from 99 to 70 wt% led to a slight
decrease both in conversion (from 95 to 83%) and
selectivity (from 91:9 to 85:15), which suggests that
the other components present in the crude oleic acid
altered the catalytic species during the course of the
reaction.
1
2
3
4
IrCl(CO)(PPh3)2 (2)
[Ir(COD)Cl]2 (1)
[Ir(COD)Cl]2 (2.5) PPh3 (15)
IrCl(CO)(PPh3)2 (2)
[Ir(COD)Cl]2 (1)
[Ir(COD)Cl]2 (1)
[Ir(COD)Cl]2 (1)
[Ir(COD)Cl]2 (1)
–
240 69
240 55
240 90
1:99
24:76
1:99
–
–
–
–
–
PPh3 (8)
–
200
0
5
PPh3 (8)
TPPTS (10)
p-(tris-Me)-TPPTS (10) 240 <5
p-(tBu)-TPPDS (10) 240 <5
200 <5
240 <5
6[d]
7[d]
8[d]
[a] Reaction conditions: 2.0 mmol oleic acid 88% (1b’), KI (20 mol%), 5 h. [b] Molar
percentage with respect to the substrate. [c] Determined by 1H NMR spectroscopy.
[d] CTAB (10 mol%), 0.5 mL water.
Kinetic profiles were plotted for 1b, 1b’, and 1b’’
(Figure 1), and S-shaped curves were obtained for
each. The change in the slope before 2 h reaction
time probably corresponds to the formation of fatty
anhydride compounds (induction period) as de-
lyst, the conversion was rather good (69%) but internal alkenes
were formed almost exclusively during the course of the reac-
tion (Table 4, entry 1). If a PPh3/[Ir(COD)Cl]2 combination was
used, better selectivity could be obtained but the conversion
decreased concurrently (Table 4, entry 2). With a higher propor-
tion of Ir precursors (5 mol%) and PPh3 (15 mol%), a high con-
version was reached but internal alkenes were mainly formed
(Table 4, entry 3). At lower temperatures (Table 4, entries 4 and
scribed previously.[6c] Notably, for a given purity, the 2/3 selec-
tivity did not evolve with time.
The catalytic experiments were then extended to the Ir-cata-
lyzed decarbonylation of other biosourced unsaturated sub-
strates (Table 7). Compared to oleic acid, very similar conver-
sions and selectivities were obtained for other biosourced sub-
strates, regardless of their nature or their purity, which high-
lights the wide scope of the studied process.
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Table 6. Effect of the substrate purity on the 2/3 selectivity.[a]
Entry
Substrate
Conversion[b]
[%]
2/3 selectivity[b]
1
2
3
oleic acid 99% (1b)
oleic acid 88% (1b’)
oleic acid 70% (1b’’)
95
90
83
91:9
87:13
85:15
[a] Reaction conditions: 1.0 mmol substrate, [Ir(COD)Cl]2 (2.5 mol%), PPh3
(15 mol%), KI (50 mol%), 2.0 mmol acetic anhydride, 1608C, 5 h. [b] De-
1
termined by H NMR spectroscopy and confirmed by GC.
Figure 1. Variation of the conversion with time for pure (1b) and crude (1b’
and 1b’’) oleic acids. Reaction conditions: 1.0 mmol substrate, [Ir(COD)Cl]2
(2.5 mol%), PPh3 (15 mol%), 2 mmol acetic anhydride, 1608C, 5 h. Conver-
The catalytic performances obtained with 10-undecenoic
acid 1,18-octadec-9-enedioic acid (diacid C18), 1,20-eicos-10-
enedioic acid (diacid C20), 1,26-hexacos-12-enedioic acid (diacid
C26), and sebacic acid (Table 7, entry 3–7) were of particular in-
terest as the resulting terminal dialkenes could be functional-
ized to access a wide range of derivatives, especially difunc-
tionalized monomers.
1
sion determined by H NMR spectroscopy and confirmed by GC.
oleic acid within 15 h led to 77% conversion and a 2/3 selec-
tivity of 73:27. After the residual acetic acid and acetic anhy-
dride were removed by distillation, the so-formed olefins (38%
yield) were recovered with a 98% purity by distillation at
2008C under reduced pressure.
Recycling experiments were performed (Table 8). The opti-
mized catalytic system could be recycled either by
simple decantation or by using a Kugelrohr distilla-
Table 7. Ir-catalyzed decarbonylation of biosourced fatty acids.[a]
tion apparatus. For example, vacuum distillation of
the crude reaction mixture could be achieved readily,
which allowed the complete elimination of residual
solvent and the recovery of analytically pure olefins
and a residue that contained unreacted substrate
and the Ir catalyst. Although a high distillation tem-
perature was required (2008C for 15–30 min), the cat-
alytic species was rather stable. Similar selectivities in
terminal alkenes were obtained after recycling, al-
though the conversions were affected significantly
probably because of the various manipulations and
the subsequent ligand oxidation (Table 8, entries 2, 5,
8, and 11). Indeed, a small proportion of oxidized
phosphanes was detected in the 31P NMR spectra of
the reaction solutions (Supporting Information). How-
ever, the decrease in conversion could be partially
overcome by the addition of fresh PPh3 (up to
5 mol%, Table 8, entries 3, 6, 9, and 12). Ionic liquids
such as 1-butyl-3-methylimidazolium bis-trifluorme-
thanesulfonimide (BMImCF3SO2) were also used to re-
cycle the catalytic system. Although the conversion
was somewhat lower than that measured in homoge-
nous conditions using PPh3 as a phosphane (84 vs.
90%), the partition of PPh3 into the upper organic
phase and the lower ionic liquid phase prevented the
reusability of the catalyst (Supporting Information).
The combination of BMImCF3SO2 and sulfonated li-
gands such as TPPTS or p-(tris-Me)-TPPTS to retain
the catalyst in the ionic liquid phase had a deleterious
effect on the conversion (<5%).
Entry
Substrate
Conversion[b]
[%]
2/3 selectivity[b]
1
2
3
92
90
85
86:14
89:11
86:14
linolenic acid 47% (1c)
erucic acid 87% (1d)
10-undecenoic acid 98% (1e)
4
5
6
88
86
79
84:16
86:14
80:20
diacid C18 99% (1 f)
diacid C20 98% (1g)
diacid C26 95% (1h)
7
8
9
65
86
84
82:18
85:15
90:10
sebacic acid 99% (1i)
ricinoleic acid 82% (1j)
An experiment was performed to assess the scale-
up of the studied catalytic system. The reaction was
performed using 100 g oleic acid (88%), 1 mol%
[Ir(COD)Cl]2, 10 mol% PPh3, 50 mol% KI, and
200 mol% Ac2O. At 1608C, the decarbonylation of
hydrogenated ricinoleic acid 85% (1k)
[a] Reaction conditions: 1.0 mmol substrate, [Ir(COD)Cl]2 (2.5 mol%), PPh3 (15 mol%),
KI (50 mol%), 2.0 mmol acetic anhydride, 1608C, 5 h. [b] Determined by H NMR spec-
troscopy and confirmed by GC.
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Conclusions
Table 8. Recycling of the Ir catalyst.[a]
Entry
Substrate
Precursor[b]
[mol%]
Ligand
[mol%]
Run
Conversion[c]
[%]
2/3 selectivity[c]
The Ir-catalyzed decarbonylation
of a wide range of biosourced
substrates was implemented
successfully to give linear a-ole-
fins in very good yield and selec-
tivity. The purity of the sub-
strates, the nature of the Ir-coor-
dinated phosphane, and the
amounts of the additives (potas-
sium iodide and acetic anhy-
dride) were key parameters to
optimize the catalytic per-
formance. The Ir-catalyzed decar-
bonylation reaction allowed the
conversion of renewable unsatu-
rated fatty acids into valuable
polyunsaturated linear a-olefins.
The latter are of particular inter-
est for the academic and indus-
trial community as they could
1
oleic acid 88% (1b’)
oleic acid 88% (1b’)
oleic acid 88% (1b’)
oleic acid 88% (1b’)
oleic acid 88% (1b’)
oleic acid 88% (1b’)
oleic acid 70% (1b’’)
oleic acid 70% (1b’’)
oleic acid 70% (1b’’)
oleic acid 99% (1b)
oleic acid 99% (1b)
oleic acid 99% (1b)
[Ir(COD)Cl]2 (1)
–
–
PPh3 (10)
–
PPh3 (3)
PPh3 (15)
–
PPh3 (5)
PPh3 (15)
–
PPh3 (5)
PPh3 (15)
–
1
2
2
1
2
2
1
2
2
1
2
2
68
44
56
90
68
79
83
62
64
95
74
84
84:16
74:26
83:17
87:13
78:22
86:14
85:15
73:27
84:16
91:9
2[d]
3[d]
4
[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 (2.5)
–
5[e]
6[e]
7
8[f]
9[f]
10
11[g]
12[g]
82:18
90:10
PPh3 (5)
[a] Reaction conditions: 1.0 mmol oleic acid (1b, 1b’, or 1b“), 2 mmol acetic anhydride, KI (50 mol%), 1608C,
5 h. [b] Numbers in parentheses correspond to molar percentage with respect to the substrate. [c] Determined
by 1H NMR spectroscopy. [d] Second run performed with the catalyst solution recovered from run 1: new sub-
strate loading (1 mmol). [e] Second run performed with the catalyst solution recovered from run 4: new sub-
strate loading (1 mmol). [f] Second run performed with the catalyst solution recovered from run 7: new sub-
strate loading (1 mmol). [g] Second run performed with the catalyst solution recovered from run 10: new sub-
strate loading (1 mmol).
give access to unknown products with potentially interesting
properties.
Experimental Section
General procedure
All reactions involving metal-phosphine catalysts were performed
under an inert atmosphere using standard Schlenk techniques. Ir,
Rh, and Pd precursors were purchased from Strem Chemicals and
1
used as received. Fatty substrates were supplied by ITERG. H and
13C NMR spectra were recorded by using a Bruker AC-300 spec-
1
trometer. H and 13C chemicals shifts were determined using resid-
ual signals of the deuterated solvents and were calibrated versus
SiMe4. Assignment of the signals was performed using 1D (1H,
13C{1H}) and 2D (COSY, HMBC, HMQC) NMR spectroscopy. Gas–
liquid chromatography with flame ionization detection (GLC–FID)
was performed by using a PerkinElmer Clarus 500 apparatus
equipped with a Varian column (VF-1 ms, 30 m/0.2 5 mm/0.25 mm,
CP8912). All products were analyzed by GC using the same
method: detector FID at 2808C; injection port temperature at
2508C; program: hold 1 min at 508C, ramp 78CminÀ1 to 1508C,
ramp 48CminÀ1 to 2508C and hold 10 min at 2508C. Hexadecane
was used as internal standard. The GC analysis allows access to the
selectivity of the substrate whatever the starting mixture.
Scheme 2. Proposed mechanism for the decarbonylation of unsaturated
fatty acids.
Given the above results, it is clear that the presence of a
C=C bond on the fatty chain of the substrate does not modify
the catalytic process significantly. Accordingly, the proposed
mechanism for the decarbonylation and isomerization of unsa-
turated fatty acids is inspired from those described previously
(Scheme 2).[36,40,41,43] In the first step, the acid anhydride 1’ is
generated in situ by the condensation reaction of carboxylic
acid 1 and Ac2O.[41] The IrI complex that results from the [Ir(-
COD)Cl]2/phosphine ligand/KI combination reacts with 1’ to
give the acyl iridium complex A.[45] The decarbonylation of A
affords the alkyl iridium complex B,[41,42] which then undergoes
b-hydride elimination to give a-olefin 2. The iridium hydride
species B may also catalyze the isomerization of the 2 formed
initially to produce internal olefin 3.[46]
Chemicals
Catalysts and additives were purchased from Sigma–Aldrich. Sub-
strates were provided by the Institute des Corps Gras (ITERG,
Pessac, France). All materials were used as received without any
further purification.
General procedure for decarbonylation-dehydration
reactions
Typically, oleic acid 99% (1b, 283 mg, 1.0 mmol), [Ir(COD)Cl]2
(17 mg, 0.025 mmol), PPH3 (39 mg, 0.15 mmol), KI (84 mg,
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0.5 mmol), and a magnetic stirring bar were added under nitrogen
in a test tube carousel. The test tube was evacuated and subse-
quently flushed several times with nitrogen. The reaction mixture
was stirred at RT for 30 min. Then, anhydride acetic (204 mg,
2 mmol) was added, and the reaction mixture was heated at 1608C
for 5 h. After the appropriate reaction time, the test tube was
cooled to RT, and the mixture was purified by flash chromatogra-
phy on silica gel (heptane) to give the corresponding olefins (95%,
2b/3b=91:9). The linear/branched (2/3) regioselectivity of olefins
(8Z, 11Z, 14Z)-Heptadeca-1,8,11,14-tetraene from linolenic
acid 47% (1c)
Obtained as an inseparable mixture (2c/3c); colorless oil. Some
other byproducts were observed that result from other fatty
acids present in the technical-grade starting material.1H NMR
(CDCl3, 300 MHz, 238C): d=5.95–5.77 (m, 1H, CH=CH2), 5.54–5.29
(m, 6H, CH=CH), 5.09–4.91 (m, 2H, CH=CH2), 2.90–2.66 (m, 4H,
=CÀCH2ÀC=), 2.25–1.97 (m, 6H, CH2ÀCH=CH), 1.50–1.21 (m, 6H,
CH2), 0.92 ppm (t, J=7.5 Hz, 3H, CH3); 13C NMR (CDCl3, 75 MHz,
238C): d=139.0, 131.8, 130.1, 128.3, 128.2, 127.7, 127.1, 114.1, 33.7,
29.5, 28.8, 28.7, 27.1, 25.6, 25.5, 20.5, 14.2 ppm.
1
was determined by H NMR spectroscopy and confirmed by GLC.
Typical procedure for product extraction and catalyst
recycling
(Z)-Pentacosa-1,12-diene from erucic acid 87% (1d)
After the appropriate reaction time, the test tube that contained
the reaction mixture was cooled to RT, and two different phases
were obtained by simple decantation. Once the phase that con-
tained the pure decarbonylation-dehydration products and the re-
sidual substrate was extracted, the phase that contained the cata-
lyst dissolved in acetic acid was recovered under an inert atmos-
phere and was reused for another run. Oleic acid (1.0 mmol), fresh
ligand PPh3 (0.05 mmol), and acetic anhydride (2 mmol) were
added under nitrogen in the test tube and stirred at 1608C for an-
other 5 h.
Obtained as an inseparable mixture (2d/3d); colorless oil. Some
other byproducts were observed that result from other fatty acids
present in the technical-grade starting material. 1H NMR (CDCl3,
300 MHz, 238C): d=5.93–5.76 (m, 1H, CH=CH2), 5.49–5.27 (m, 2H,
CH=CH), 5.08–4.90 (m, 2H, CH=CH2), 2.13–1.92 (m, 6H, CH2ÀCH=
CH), 1.48–1.20 (m, 26H, CH2), 0.91 ppm (t, J=6.6 Hz, 3H, CH3);
13C NMR (CDCl3, 75 MHz, 238C): d=139.3, 130.0, 129.9, 114.0, 33.8,
31.9, 29.8, 29.7, 29.6, 29.6, 29.5, 29.5, 29.4, 29.3, 29.1, 28.9, 27.2,
22.7, 14.1 ppm.
Deca-1,9-diene from 10-undecenoic acid 98% (1e)
1
Typical procedure for product distillation and catalyst
recycling
Obtained as an inseparable mixture (2e/3e); colorless oil. H NMR
(CDCl3, 300 MHz, 238C): d=5.96–5.78 (m, 2H, CH=CH2), 5.09–4.98
(m, 4H, CH=CH2), 2.21–1.99 (m, 4H, CH2ÀCH=CH), 1.57–1.31 ppm
(m, 8H, CH2); 13C NMR (CDCl3, 75 MHz, 238C): d=139.1, 114.9, 33.8,
29.7, 29.6 ppm.
The crude decarbonylation-dehydration reaction mixture was trans-
ferred under an inert atmosphere into a 20 mL flask and was dis-
tilled by using a Kugelrohr system. The first step consisted of the
removal of the residual acetic acid and acetic anhydride under re-
duced pressure 10 mmHg at 808C. In the second step, the temper-
ature was raised to 2008C at 10 mmHg. The pure decarbonylation-
dehydration products were collected in the distillation flask, and
the catalyst remained in solution with residual fatty acids in the
boiler. This residual catalytic phase was collected under inert at-
mosphere and reused, with or without the addition of fresh ligand,
for another decarbonylation run.
(Z)-Hexadeca-1,7,15-triene from 1,18-octadec-9-enedioic
acid (diacid C18) 99% (1 f)
1
Obtained as an inseparable mixture (2 f/3 f); colorless oil. H NMR
(CDCl3, 300 MHz, 238C): d=5.94–5.77 (m, 2H, CH=CH2), 5.54–5.33
(m, 2H, CH=CH), 5.10–4.92 (m, 4H, CH=CH2), 2.17–1.95 (m, 8H,
CH2ÀCH=CH), 1.53–1.26 ppm (m, 12H, CH2); 13C NMR (CDCl3,
75 MHz, 238C): d=139.2, 130.6, 130.5, 114.5, 33.8, 32.5, 29.5, 28.8,
28.7 ppm.
1-Heptadecene from stearic acid 98% (1a)
1
(Z)-Octadeca-1,9,17-triene from 1,20-eicos-10-enedioic acid
Obtained as an inseparable mixture (2a/3a); colorless oil. H NMR
(diacid C20) 98% (1g)
(CDCl3, 300 MHz, 238C): d=5.86–5.77 (m, 1H, CH=CH2), 5.01–4.92
(m, 2H, CH=CH2), 2.06–2.02 (m, 2H, CH2ÀCH=CH), 1.39–1.25 (m,
26H, CH2), 0.88 ppm (t, J=6.9 Hz, 3H, CH3); 13C NMR (CDCl3,
75 MHz, 238C): d=139.2, 114.1, 33.9, 32.0, 29.9, 29.8, 29.8, 29.8,
29.7, 29.7, 29.6, 29.5, 29.4, 29.2, 29.0, 22.7, 14.1 ppm.
1
Obtained as an inseparable mixture (2g/3g); colorless oil. H NMR
(CDCl3, 300 MHz, 238C): d=5.94–5.77 (m, 2H, CH=CH2), 5.53–5.32
(m, 2H, CH=CH), 5.09–4.90 (m, 4H, CH=CH2), 2.16–1.91 (m, 8H,
CH2ÀCH=CH), 1.51–1.21 ppm (m, 16H, CH2); 13C NMR (CDCl3,
75 MHz, 238C): d=139.4, 130.2, 130.2, 114.0, 33.8, 32.6, 29.6, 29.5,
29.0, 28.9 ppm.
(Z)-Heptadeca-1,8-diene from oleic acid 88% (1b)
Obtained as an inseparable mixture (2b/3b); colorless oil. Some
other byproducts were observed that result from other fatty acids
present in the technical-grade starting material. 1H NMR (CDCl3,
300 MHz, 238C): d=5.92–5.77 (m, 1H, CH=CH2), 5.49–5.30 (m, 2H,
CH=CH), 5.09–4.89 (m, 2H, CH=CH2), 2.17–1.94 (m, 6H, CH2ÀCH=
CH), 1.50–1.23 (m, 18H, CH2), 0.92 ppm (t, J=6.9 Hz, 3H, CH3);
13C NMR (CDCl3, 75 MHz, 238C): d=139.2, 130.0, 129.8, 114.1, 33.8,
31.9, 29.8, 29.7, 29.6, 29.5, 29.3, 28.9, 28.8, 27.0, 27.1, 22.7,
14.1 ppm.
(Z)-Tetracosa-1,12,23-triene from 1,26-hexacos-12-enedioic
acid (diacid C26) 95% (1h)
1
Obtained as an inseparable mixture (2h/3h); colorless oil. H NMR
(CDCl3, 300 MHz, 238C): d=5.96–5.76 (m, 2H, CH=CH2), 5.51–5.34
(m, 2H, CH=CH), 5.11–4.92 (m, 4H, CH=CH2), 2.14–1.92 (m, 8H,
CH2ÀCH=CH), 1.49–1.20 ppm (m, 28H, CH2); 13C NMR (CDCl3,
75 MHz, 238C): d=139.4, 130.2, 130.2, 114.2, 33.8, 32.6, 31.9, 29.7,
29.6, 29.4, 29.2, 28.9, 27.7 ppm.
&
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Octa-1,8-diene issued from sebacic acid 99% (1i)
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(CDCl3, 300 MHz, 238C): d=5.91–5.79 (m, 2H, CH=CH2), 5.10–5.02
(m, 4H, CH=CH2), 2.15–1.99 (m, 4H, CH2ÀCH=CH), 1.52–1.43 ppm
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29.7 ppm.
(R,Z)-Heptadeca-9,16-dien-7-yl acetate from ricinoleic acid
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Obtained as an inseparable mixture (2k/3k); colorless oil. The final
product obtained is the acetate version because of the esterifica-
tion of the alcohol. Some other byproducts were observed that re-
sulted from other fatty acids present in the technical-grade starting
material. 1H NMR (CDCl3, 300 MHz, 238C): d=5.93–5.75 (m, 1H,
CH=CH2), 5.57–5.28 (m, 2H, CH=CH), 5.08–4.90 (m, 2H, CH=CH2),
4.97–4.81 (m, 1H, CHÀOCOCH3), 2.42–2.18 (m, 2H, C=CÀCH2ÀCHÀ
OH), 2.18 (s, 3H, CH3acetate), 2.18–1.92 (m, 4H, CH2ÀCH=CH), 1.73–
1.21 (m, 16H, CH2), 0.92 ppm (t, J=6.9 Hz, 3H, CH3); 13C NMR
(CDCl3, 75 MHz, 238C): d=170.8, 139.0, 132.7, 124.2, 114.1, 73.9,
33.9, 33.6, 31.9, 31.7, 29.7, 29.5, 29.1, 28.8, 27.3, 25.4, 22.6, 21.3,
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´
´
ˇ
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product obtained is the acetate version because of the esterifica-
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CH=CH2), 5.08–4.91 (m, 2H, CH=CH2), 4.97–4.81 (m, 1H, CHÀ
OCOCH3), 2.13 (s, 3H, CH3acetate), 2.13–1.98 (m, 2H, CH2ÀCH=CH),
1.61–1.46 (m, 4H, CH2ÀCHOH), 1.46–1.17 (m, 20H, CH2), 0.91 ppm
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139.4, 114.2, 74.4, 34.1, 33.8, 31.8, 29.7, 29.4, 29.2, 28.9, 27.6, 25.3,
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renewable resources
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Received: February 9, 2015
Revised: March 24, 2015
Published online on && &&, 0000
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FULL PAPERS
The future for olefins: Ir catalysts are
suitable to decarbonylate a wide range
of biosourced substrates into linear a-
olefins under rather mild conditions.
Optimization of the catalytic system
leads to very high conversion and selec-
tivity in terminal alkenes, while the cata-
lytic Ir system can be efficiently recy-
cled. The scaling-up of the studied cata-
lytic system has been successfully per-
formed, still affording good conversion
and selectivity in terminal olefins.
J. Ternel, T. Lebarbꢀ, E. Monflier, F. Hapiot*
&& – &&
Catalytic Decarbonylation of
Biosourced Substrates
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