Tandem catalytic acrylonitrile cross-metathesis and hydrogenation of nitriles with ruthenium catalysts: Direct access to linear α,ω- aminoesters from renewables

Article abstract of DOI:10.1002/cssc.201200086

Fraternité, Solidarité & complémentarité en Catalyse: Tandem alkene cross-metathesis of acrylonitrile with long-chain alkene and hydrogenation catalysis is performed by using a single ruthenium-alkylidene catalyst precursor. The protocol allows the catalytic transformation of unsaturated fatty acids, derivatives of plant oils, into α,ω-aminoesters. A key step involves the reduction of nitrile-ester intermediates into aminoesters, the precursors of polyamides, with alkene metathesis catalyst residue under mild conditions. Copyright

Full text of DOI:10.1002/cssc.201200086

DOI: 10.1002/cssc.201200086
Tandem Catalytic Acrylonitrile Cross-Metathesis and Hydrogenation of
Nitriles with Ruthenium Catalysts: Direct Access to Linear a,w-Aminoesters
from Renewables
Xiaowei Miao,[a] Cꢀdric Fischmeister,[a] Christian Bruneau,*[a] Pierre H. Dixneuf,*[a] Jean-Luc Dubois,[b] and Jean-
Luc Couturier[b]
Dedicated to Prof. Hubert Le Bozec, a pioneer in the field of metal complexes for nonlinear optics, on the occasion of his 60th birthday.
The development of single catalyst precursors capable of per-
forming multiple, mechanistically distinct reactions to reach
complex molecular architectures as well as useful industrial
chemicals and materials using more straightforward methods
is a challenge.[1] Such developments require the discovery of
catalyst systems that can be applied to a useful catalytic trans-
formation of industrial importance. Such catalysts also contrib-
ute to the creation of economical processes with greener
aspects, and have the potential to achieve more efficient trans-
formations of renewables. The objective of our work is to pres-
ent the production of a,w-amino esters, precursors of polyam-
ides, from renewable plant oil derivatives by using a catalytic
system that is able to perform two consecutive catalytic
reactions.
of secondary and tertiary amines,[9] but it has not been strong-
ly investigated until now. Only a few examples have shown to
be very selective in producing the primary amines.[9a,10,11,12]
Whereas rhenium-nitrosyl catalysts favor hydrogenation of ni-
triles into secondary amines,[9c] Hidai and co-workers have re-
ported improvements in the efficiency and selectivity for the
hydrogenation of benzonitrile to benzylamine by addition of
catalytic amounts of alkoxide base to a ruthenium amido com-
plex at 808C and 30 bar of H2.[10b] Morris[11a] has applied a ruthe-
nium hydride complex [Ru(H)(Cl){PPh2[(ortho-C6H4)CH2NHCH2-
]}2] with tBuOK that promotes the selective catalytic nitrile hy-
drogenation of benzonitrile at 208C under 14 bar of H2. Leitner
and co-workers, using a pincer ruthenium-hydride catalyst,
have shown that high selectivity in primary amines could be
obtained, especially with water added to toluene, under 75 bar
H2 at 1358C for 24–45 h,[10c] and Sabo-Etienne et al. have hy-
drogenated benzonitrile into benzylamine under mild condi-
tions (RT, 3 bar H2, 2–24 h) using [RuH2(H2){P(cyclopentyl)3}2]
catalyst.[11b] It is noteworthy that the latter catalysts operate
without base additives. Recently, Beller et al.[12] have reported
Polyamides occur in nature as proteins, leading to wool and
silk, but are especially the basis of thermohardening resins and
synthetic fibers with many applications, for example in sport
equipment.[2] Industrially they are commonly synthesized from
monomers derived from petroleum products, such as dia-
mines, diacids, and aminoacids.[3] This increasing interest in
polyamides has recently motivated the search for processes of-
fering, at least, a partial new supply to polyamide precursors
from renewable resources,[4] rather than from fossil sources.
Recently, a first step in this direction has been made by cross-
metathesis transformations of unsaturated acid derivatives aris-
ing from plant oils with functional olefins[5] into bifunctional
fatty esters, including a,w-nitrile esters.[6] However, the hydro-
genation of the nitrile functionality associated to metathesis
remains a challenge for the production of amines, as the nitrile
hydrogenation in industry is mainly performed with heteroge-
neous reducing catalysts such as Raney cobalt or nickel,[7] but
usually with moderate selectivity.[8]
that
a
commercially available ruthenium complex
[Ru(cod)(methylallyl)2] (cod=1,5-cyclooctadiene) catalyzed the
hydrogenation of various nitriles in the presence of both
a phosphine ligand and tBuOK at 80–1408C and 50 bar of H2
to afford the corresponding amines with good to excellent
yields.[12b] They have also shown that milder conditions could
be obtained through replacement of phosphine ligands by N-
heterocyclic carbenes.[12c] They demonstrated that the addition
of NH4Cl increases the selectivity towards the production of
primary amines by inhibiting their further transformation into
secondary amines. For unsaturated fatty nitriles, for example,
that of beef tallow derivatives, hydrogenation into amines has
been performed with a carbon-modified nickel catalyst to
retain double bonds.[7g]
The catalytic homogeneous hydrogenation of nitriles repre-
sents a potentially valuable route to primary amines. However,
it requires drastic conditions and brings difficulty in isolating
the target compounds due to side products consisting mainly
Recently, we have reported a tandem ruthenium-catalyzed
cross-metathesis (CM) hydrogenation of unsaturated esters de-
rived from plant oil derivatives, which provided saturated ni-
trile-acid and ester compounds,[6a] thus retaining the non-hy-
drogenated nitrile functionality. In this work it was shown that
following the cross-metathesis step, the ruthenium alkylidene
metathesis catalyst was totally consumed and that the residual
ruthenium species was still an efficient hydrogenation catalyst.
Whereas the cross-metathesis conditions of long-chain alkenes
with acrylonitrile have been discovered,[6] the consecutive cata-
lytic hydrogenation into amines has not been investigated.
[a] Dr. X. Miao, Dr. C. Fischmeister, Dr. C. Bruneau, Prof. P. H. Dixneuf
Organomꢀtalliques: Matꢀrieux et Catalyse
Institut Sciences Chimiques de Rennes
UMR 6226 CNRS-Universitꢀ de Rennes
Campus de Beaulieu, 35042 Rennes (France)
[b] Dr. J.-L. Dubois, Dr. J.-L. Couturier
ARKEMA, CRRA,
BP 63 Rue Henri Moissan, 69493, Pierre Bꢀnite (France)
Supporting Information for this article is available on the WWW under
http://dx.doi.org/10.1002/cssc.201200086.
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formed in moderate yield (entries 2, 3). Thus, besides
the addition of tBuOK, the influence of some other
additives, such as bidentate phosphorus-containing
ligands, ammonium chloride or co-solvents, was then
examined (entries 4–9). The conversion of 2 into 4
was decreased by each additive and all tests led to
lower yields of the target product 4. More specifically,
the addition of 1,2-bis(diphenylphosphino)ethane
even inhibited the hydrogenation step from 2 into 3
(entry 4). Ammonium chloride, usually used to pre-
vent secondary amines formation,[8c,10b,12] actually decreased
the selectivity into long-chain primary amine as only 64% of
monoalkylamine 4 was obtained (entry 6). Transesterification of
3 occurred in the reaction with iPrOH applied as co-solvent
(entry 9).
Scheme 1. Tandem cross-metathesis and hydrogenation to produce linear a,w-amino
acids/esters.
We now report for the first time that following the rutheni-
um–alkylidene-catalyzed cross-metathesis of alkenes with acryl-
onitrile (Scheme 1, step a) the residual ruthenium species can
be used for the direct catalytic hydrogenation of the formed
nitriles with high selectivity into primary amines (step b), and
that the tandem catalytic cross-metathesis–hydrogenation re-
actions of unsaturated fatty esters compounds allow the direct
formation of a,w-linear aminoester monomers. The latter are
precursors for the production of polyamides from renewable
resources.[13]
The amount of tBuOK and hydrogenation time for selective
conversion were also investigated (Table 1, entries 10–14).
Increasing the amount of base up to 30 mol% with 20 bar of
initial hydrogen pressure led to 92% yield of 4 (entry 11). At
higher base concentrations, a slight decrease in activity was
observed (entry 12). With shorter reaction times of 16–24 h,
the conversion of 3 into 4 was observed in lower yield (en-
tries 13–14). A metal-free blank hydrogenation test was per-
formed on isolated 2 in toluene at 808C under 30 bar of H2 in
the presence of 30 mol% of tBuOK. After 48 h, no conversion
could be detected, thus confirming the involvement of the re-
sidual ruthenium species in the nitrile reduction step. Notably,
with the most efficient conditions (entry 11), whereas primary
alkylamines formation usually leads to secondary and even ter-
tiary alkylamine by-products, only the primary amine 4 was
formed with this catalyst system without the requirement for
addition of NH4Cl.
Our initial studies were carried out with methyl undec-10-
enoate 1 derived from castor oil[14] with 2 equivalents of acrylo-
nitrile using 3 mol% of Grubbs–Hoveyda 2nd generation cata-
lyst I in toluene (Scheme 2).
Having demonstrated the best result obtained by using
Grubbs–Hoveyda catalyst I for the cross-metathesis step and
the hydrogenation step promoted by the ruthenium catalyst
Scheme 2. Ruthenium-alkylidene olefin metathesis catalysts evaluated for
acrylonitrile cross-metathesis and subsequent hydrogenation.
Following the cross-metathe-
Table 1. Influence of additives on the hydrogenation step.[a]
sis reaction performed at 1008C
for 1 h, the crude reaction mix-
ture containing the ruthenium
catalyst was transferred into an
autoclave and charged with H2.
The results are shown in Table 1.
The first attempt was run with-
out any additive at 808C with
30 bar of H2 for 48 h. Notably,
no aminoester was observed,
but methyl 11-cyanoundeca-
noate (3) was isolated as the
Entry
tBuOK
[mol%]
Additive
Amount
[mol%]
H2
[bar]
t
[h]
GC yield
(isolated yield) [%]
2
3
4
1
2
3
4
5
6
7
8
–
–
–
–
–
–
–
30
30
20
20
20
20
20
20
20
20
20
20
20
20
48
48
48
44
44
48
44
44
44
48
44
48
16
24
–
–
–
71
–
–
–
–
–
–
–
–
–
–
93 (90)
10
15 (10)
23
–
15
15
15
15
15
15
30
30
10
30
60
30
30
79 (65)
74 (60)
–
5
64
31
–
dppe[b]
dppb[c]
NH4Cl
MeOH
DMC[d]
iPrOH
–
6 mol%
6 mol%
10 mol%
5 mL
5 mL
5 mL
–
–
–
–
–
86
8
33
93
80[e]
22
9
8
10
11
12
13
14
65
92 (85)
88
25
45
sole
product
(Scheme 3);
–
–
–
–
–
–
Table 1, entry 1]. To access the
formation of aminoester, the in-
fluence of the addition of potas-
sium tert-butoxide to the cata-
lyst was investigated. Indeed, in
the presence of tBuOK, methyl
12-aminododecanoate (4) was
67
44
[a] Reaction conditions: 0.5 mmol of 1, 1 mmol of acrylonitrile, 0.015 mmol of Grubbs-Hoveyda 2nd generation
(I), 10 mL of toluene for 1st step; 20–30 bar H2, 808C, 15–60 mol% of tBuOK for the 2nd step. [b] dppe=
Ph2PCH2CH2PPh2. [c] dppb=Ph2P(CH2)4PPh2. [d] DMC=dimethyl carbonate). [e] Isopropyl nitrile ester was isolat-
ed instead of 3.
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entry 8). The reaction with
Grubbs 2nd generation catalyst
III neither offered a high yield of
2 at the cross-metathesis step
(74% quantitatively transformed
into 3) nor good selectivity to
aminoester in the sequential hy-
drogenation step (entries 9, 10).
Scheme 3. Tandem catalytic ester 1/acrylonitrile cross-metathesis and hydrogenation.
The influence of the initial cata-
lyst loading was vital, the reac-
tion with 1 mol% instead of
residue in the presence of 30 mol% of tBuOK, 20 bar of H2
(Table 1, entry 11), we examined the influence of different
bases on the yield of aminoester under the same reaction con-
ditions (Table 2, entries 1–5). The reaction with addition of po-
3 mol% of I yielded only 10% of aminoester 4, and 3 was ob-
tained as major product; however, no other byproduct was ob-
served. It is noteworthy that without the use of the base in the
second step, the hydrogenation of the C=C bond is selective
whereas the presence of a coordinating base further favors re-
duction of the nitrile into amine.
Table 2. Influence of base nature and initial olefin metathesis catalyst
precursor on the production of aminoester 4.[a]
Another possible approach to C12 a,w-nitrile-ester 3 and
then a,w-aminoester 4 would involve the tandem cross-meta-
thesis with methyl acrylate of undec-10-enenitrile 5, readily ob-
tained from ammoniation of undecylenic acid,[15] and then the
sequential catalytic hydrogenation of the nitrile-ester inter-
mediate 6 with the ruthenium catalyst residue (Scheme 4).
Thus, the reaction of 5 with 2 equiv methyl acrylate was per-
formed in toluene for 1 h at 1008C using 3 mol% of ruthenium
catalyst I. The reaction led to complete transformation of 5
into the two stereoisomers of 6. Then the reaction mixture was
transferred into an autoclave charged with 30 mol% of tBuOK,
20 bar of H2, and stirred at 808C for 40 h. The target aminoest-
er 4 was obtained in 96% GC yield. The conversion into 4 de-
creased to 50% when a lower amount of tBuOK (15 mol%)
was added for the sequential hydrogenation step. The initial
catalyst loading of 3 mol% was again crucial as, with an initial
loading of 1 mol%, no conversion into 4 was observed.
We found that the cross-metathesis of 5 with methyl acry-
late into unsaturated nitrile-ester 6 could proceed at room
temperature with excellent yield (>98%),[6c] thus the catalytic
hydrogenation activity of the ruthenium residue arising from
the cross-metathesis step under milder conditions was investi-
gated. The reaction of 5 with methyl acrylate using 3 mol% of
catalyst I was carried out in toluene for 1 h at room tempera-
ture. Then the reaction mixture was transferred into an auto-
clave charged with 30 mol% of tBuOK, 20 bar of H2, stirred at
808C for 40 h. As expected, the aminoester 4 was obtained in
Entry
Catalyst
precursor
Base
Amount
[mol%]
t
[h]
GC yield [%]
3
1
2
3
4
5
6
7
8
9
I
I
I
I
KOH
KOH
NaOH
Cs2CO3
LDA
60
30
60
30
30
–
15
40
15
40
67
74
67
67
74
48
45
45
48
48
–
40
–
10
82
93
–
72
74
48
I
II
II
II
III
III
–
tBuOK
tBuOK
tBuOK
tBuOK
10
[a] Reaction conditions: 0.5 mmol of 1, 1 mmol of acrylonitrile,
0.015 mmol of ruthenium catalyst, 10 mL of toluene for the 1st step;
20 bar H2, 808C, 44–67 h for the 2nd step.
tassium hydroxide, sodium hydroxide, or cesium carbonate af-
forded good to excellent yields of 4 (entries 1–4). However, the
reaction with lithium diisopropylamide, a stronger base than
tBuOK, afforded the saturated nitrile-ester compound 3 as the
major product (entry 5). The reaction with 60 mol% of KOH
provided 90% yield, whereas with only 30 mol% of KOH, 56%
yield of 4 was obtained together with 40% yield of 3 (en-
tries 1–2). The influence of the nature of the initial alkene
metathesis ruthenium catalyst was also of interest to investi-
gate (entries 6–10). The tandem
cross-metathesis and hydroge-
nation with the new ruthenium
complex II, the so-called Umi-
core M51, provided similar re-
sults to the Grubbs–Hoveyda
complex I but with the advant-
age of requiring only 15 mol%
of tBuOK (entry 7), instead of
30 mol% in the case with
I
(Table 1, entry 11). Increasing the
base concentration gave a de-
crease of the yield of 4 (Table 2,
Scheme 4. Tandem catalytic nitrile 5/methyl acrylate cross-metathesis and hydrogenation.
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Acknowledgements
The authors are grateful to
Arkema and ANRT for a CIFRE
Ph.D. grant to X.M., to CNRS,
French Ministry MESR, the Euro-
pean Network IDECAT and to the
Institut Universitaire de France
(PHD) for support, and to Umi-
core Company for fruitful discus-
sions.
Scheme 5. Sequential catalytic synthesis of aminoester 10 from diester 7.
97% GC and 90% isolated yields. The catalytic amount of
tBuOK in this case could be decreased to 20 mol%, and the hy-
drogenation of both C=C and CN groups still remained highly
efficient (95% GC yield).
Keywords: fatty esters
renewable resources · ruthenium
· hydrogenation · metathesis ·
The comparison of tandem cross-metathesis/hydrogenation
of both renewable unsaturated ester 1 (Scheme 3) and nitrile 5
(Scheme 4) shows that they are very competitive to reach the
same C12 aminoester via these catalytic tandem reactions.
The tandem catalytic reactions, cross-metathesis with acrylo-
nitrile/hydrogenation, were then applied to the renewable
fatty compound 7 as an attempt to produce the C11 a,w-ami-
noester 10 (Scheme 5). The reaction of (Z)-dimethyl octadec-9-
enedioate 7, obtained via bioconversion of sunflower oil[16] or
self-metathesis of oleic acid derivatives,[17] with 4 equivalents
of acrylonitrile was performed in toluene for 2 h and using
6 mol% of catalyst I, considering the relative catalyst precursor
loading for the formation of two molecules of unsaturated ni-
trile-ester 8 from 7. Then the reaction mixture was transferred
into an autoclave charged with 60 mol% of tBuOK, 20–30 bar
of H2, and stirred at 808C for 48 h (Scheme 5). C11 aminoester
monomer 10 was obtained in 89% GC yield (78% isolated
yield) from the reaction with 30 bar of H2. A decrease of initial
catalyst I loading to 3 mol% led only to 25% of isolated yield
of 10 and 47% of saturated nitrile-ester compound 9.
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Received: February 2, 2012
Revised: April 10, 2012
Published online on && &&, 0000
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COMMUNICATIONS
X. Miao, C. Fischmeister, C. Bruneau,*
P. H. Dixneuf,* J.-L. Dubois, J.-L. Couturier
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Tandem Catalytic Acrylonitrile Cross-
Metathesis and Hydrogenation of
Nitriles with Ruthenium Catalysts:
Direct Access to Linear a,w-
Fraternitꢀ, Solidaritꢀ & complꢀmentar-
itꢀ en Catalyse: Tandem alkene cross-
metathesis of acrylonitrile with long-
chain alkene and hydrogenation cataly-
sis is performed by using a single ruthe-
nium-alkylidene catalyst precursor. The
protocol allows the catalytic transforma-
tion of unsaturated fatty acids, deriva-
tives of plant oils, into a,w-aminoesters.
A key step involves the reduction of ni-
trile-ester intermediates into aminoest-
ers, the precursors of polyamides, with
alkene metathesis catalyst residue
under mild conditions.
Aminoesters from Renewables
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www.chemsuschem.org
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ChemSusChem 0000, 00, 1 – 5
ÝÝ
These are not the final page numbers!