Efficient Palladium-Catalyzed Carbonylation of 1,3-Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters

Article abstract of DOI:10.1002/anie.202015329

The dicarbonylation of 1,3-butadiene to adipic acid derivatives offers the potential for a more cost-efficient and environmentally benign industrial process. However, the complex reaction network of regioisomeric carbonylation and isomerization pathways, make a selective and direct transformation particularly difficult. Here, we report surprising solvent effects on this palladium-catalysed process in the presence of 1,2-bis-di-tert-butylphosphin-oxylene (dtbpx) ligands, which allow adipate diester formation from 1,3-butadiene, carbon monoxide, and methanol with 97 % selectivity and 100 % atom-economy under scalable conditions. Under optimal conditions a variety of di- and triesters from 1,2- and 1,3-dienes can be obtained in good to excellent yields.

Full text of DOI:10.1002/anie.202015329

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How to cite: Angew. Chem. Int. Ed. 2021, 60, 9527–9533
International Edition: doi.org/10.1002/anie.202015329
German Edition: doi.org/10.1002/ange.202015329
Palladium Catalysis
Efficient Palladium-Catalyzed Carbonylation of 1,3-Dienes: Selective
Synthesis of Adipates and Other Aliphatic Diesters
Ji Yang, Jiawang Liu, Yao Ge, Weiheng Huang, Francesco Ferretti, Helfried Neumann,
Haijun Jiao, Robert Franke, Ralf Jackstell, and Matthias Beller*
Abstract: The dicarbonylation of 1,3-butadiene to adipic acid
derivatives offers the potential for a more cost-efficient and
environmentally benign industrial process. However, the com-
plex reaction network of regioisomeric carbonylation and
isomerization pathways, make a selective and direct trans-
formation particularly difficult. Here, we report surprising
solvent effects on this palladium-catalysed process in the
presence of 1,2-bis-di-tert-butylphosphin-oxylene (dtbpx) li-
gands, which allow adipate diester formation from 1,3-
butadiene, carbon monoxide, and methanol with 97% selec-
tivity and 100% atom-economy under scalable conditions.
Under optimal conditions a variety of di- and triesters from 1,2-
and 1,3-dienes can be obtained in good to excellent yields.
mented in the Lucite process as a reaction step for the methyl
methacrylate process.[4]
Although the underlying reactions are known for nearly
eighty years,[5] still important catalyst challenges exist in this
area, for example, the direct dicarbonylation of 1,3-butadiene
to give selectively adipate esters, which are intermediates for
bulk polyamides and polyesters produced on multi-million
ton-scale.[6] Currently, adipate diesters are used for plasti-
cizers, perfumes, lubricants, solvents, several active pharma-
ceutical ingredients (APIꢀs), and with respect to scale most
importantly for the production of polyamides (nylon).[7] So
far, adipate diesters are mainly produced in industry by
oxidation of a mixture of cyclohexanol and cyclohexanone
(so-called KA-oil) with an excess of nitric acid, followed by
esterification with the corresponding alcohols (Sche-
me 1a).[6a,8] Due to the corrosiveness of the mixture, this
process requires special equipment, and produces stoichio-
metric amounts of nitrous oxide (N2O), which has nearly 300
times the atmospheric heat-trapping capacity of CO2.[9]
Due to the intrinsic problems of the present process and
the potential benefits of a direct dicarbonylation process,
several companies all over the world including BASF,
Introduction
Due to its availability and low price, carbon monoxide is
a central intermediate in the chemical industry that is easily
produced from fossil-based resources (coal, gas).[1] In the
future, an increasing amount can be available from renew-
ables (CO2 or bio-waste).[2] Among the different carbon-
ylations, specifically reactions of olefins with CO constitute
the important applications of industrial homogeneous catal-
ysis.[1,3] In fact, nowadays more than 10 million tons of
carbonyl compounds, especially aldehydes via hydroformyla-
tion, are produced annually for many consumer products. In
addition, the so-called alkoxycarbonylation reaction allows an
atom-efficient access of esters and was industrially imple-
[*] Dr. J. Yang, Dr. J. Liu, Dr. Y. Ge, W. Huang, Dr. F. Ferretti,
Dr. H. Neumann, Dr. H. Jiao, Dr. R. Jackstell, Prof. Dr. M. Beller
Leibniz-Institut für Katalyse e. V.
Albert-Einstein-Straß e 29a,18059 Rostock (Germany)
E-mail: matthias.beller@catalysis.de
R. Franke
Evonik Operations GmbH
Paul-Baumann-Str. 1, 45772 Marl (Germany)
and
Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum
44780 Bochum (Germany)
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.202015329.
ꢀ 2021 The Authors. Angewandte Chemie International Edition
published by Wiley-VCH GmbH. This is an open access article under
the terms of the Creative Commons Attribution Non-Commercial
License, which permits use, distribution and reproduction in any
medium, provided the original work is properly cited and is not used
for commercial purposes.
Scheme 1. Selected processes for making alkyl adipates.
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Dupont, Shell, Dow, Kuraray and Sinopec investigated the
synthesis of adipate esters from 1,3-butadiene.[10] Neverthe-
less, no industrially viable process has been developed yet,
although some pilot facilities involving at least two-step
reactions were realized (Scheme 1b and c).[12] Most notable,
Drent and co-workers described a single-pot dimethoxycar-
bonylation of 1,3-butadiene in the presence of a single
catalytic system.[10k] A drawback of these processes is the
low regioselectivity for the desired linear diester, although
high selectivity has been obtained in related hydroxycarbo-
nylations.
Recently, we discovered that a particular bidentate
phosphine ligand (HeMaRaPhos) L1 allowed the palladi-
um-catalyzed dicarbonylation of 1,3-butadiene towards dia-
lkyl adipates in ꢀ 95% yield and ꢀ 97% selectivity
(Scheme 1d).[12] Crucial for the success of this ligand is the
intrinsic basic pyridyl substituent combined with a tert-butyl
group on one of the phosphorous atoms, which proved to be
essential for high activity in other palladium-catalyzed
alkoxycarbonylation reactions too.[13]
In order to understand the different reactivity of He-
MaRaPhos and 1,2-bis-di-tert-butylphosphinoxylene (L2,
dtbpx), we re-investigated the reactivity of the latter system
in more detail. Notably, L2 is commercially used in the
alkoxycarbonylation of ethylene (Lucite a-process)[4] and can
be considered as a benchmark ligand for such reactions. In our
study, we discovered a peculiar solvent effect, which laid the
basis for a new protocol for direct dicarbonylation of 1,3-
butadiene and related dienes in the presence of several
palladium catalyst systems.
HeMaRaPhos L1 or dtbpx L2 under previously optimized
conditions (1208C, 40 bar CO with p-toluenesulfonic acid as
a co-catalyst; Table 1). As expected in the presence of L1 both
reactions worked well and the desired esters were obtained
after 24 h in 86/85% yield and 97% selectivity (Table 1
entries 1–2). Surprisingly, applying L2 at similar conditions
a significantly different performance was observed depending
on the alcohol used (Table 1, entries 3–4). In case of
methanol, no desired dicarbonylation was detected and no
conversion took place at all. A similar behavior was observed
using ethanol and n-propanol (Figure S4). In contrast, using
n-butanol the corresponding di-n-butyl diester was obtained
in 80% yield and 98% selectivity. For the performance of
other alcohols see Figure S4. To understand this unusual
behavior, the reaction of 1,3-butadiene with methanol was
performed in different solvents (Table 1, entries 5–11). All
these experiments were completed in the presence of 4 equiv
of methanol. We first tested toluene, which is frequently used
in carbonylation reactions and were surprised to observe the
desired product in substantial amount. In fact, simply the
addition of toluene led to 80% of 4aa with 97% selectivity
compared to the originally non-reactive system.
Similarly, in the presence of tetrahydrofuran, heptane, and
dichloromethane, product 4aa is formed, albeit in lower yield.
Other co-solvents such as ethyl acetate and acetonitrile only
led to traces of 4aa. As toluene gave the best result among the
tested solvents, the influence of the toluene concentration on
the mono- and dicarbonylation process was investigated in
more detail. As shown in Figure 1, our recently developed
palladium catalyst system with L1 is very robust and not
affected by the concentration of methanol. Consequently,
product yields between 80 and 85% were obtained. On the
other hand, the catalyst with L2 is very sensitive with respect
to the methanol concentration and the product yield of 4aa is
increased with decreasing methanol concentration. Compar-
ing the kinetic behavior of both catalyst systems, some
peculiar differences became apparent (Figure 2). The one
containing dtbpx L2 shows a prolonged induction period
(6–8 h), while in the presence of L1 in the first two hours 3aa
Results and Discussion
At the beginning of this work, we compared the dicarbo-
nylation of 1,3-butadiene with industrially most relevant
methanol and n-butanol in the presence of Pd(TFA)2 and
Table 1: Pd-catalyzed alkoxycarbonylation of 1,3-butadiene with metha-
nol and butanol: Variation of solvents.
Entry
Ligand
Solvent
Yield [%]
Selectivity
(n-/iso-)
1
2
3
4
5
6
7
8
9
L1
L1
L2
L2
L2
L2
L2
L2
L2
L2
L2
MeOH
nBuOH
86
85
0
80
80
62
25
0
97/3
97/3
–
98/2
97/3
96/4
97/3
–
MeOH
nBuOH
toluene
THF
heptane
MeCN
CH2Cl2
31
trace
18
96/4
–
97/3
10
11
EtOAc
toluene:MeCN (1:1)
For reaction conditions and more details, see Supporting Information,
Section 3.8, Table S7.
Figure 1. Pd-catalyzed alkoxycarbonylation of 1,3-butadiene with meth-
anol in toluene.
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Figure 2. Kinetic monitoring experiments. Notes: The X-axis represents
time and the Y-axis represents yield. Conditions: Using 100 ml
autoclave with sampling function: 1,3-butadiene (gas, 1 g, 18.5 mmol),
Pd(TFA)2 (1.0 mol%), HeMaRaPhos or dtbpx ligand (2.0 mol%),
PTSA·H2O (4.0 mol%), MeOH (4 equiv to 1,3-butadiene), toluene
(27 mL), CO (40 atm), 1208C; the yields were determined by GC
analysis.
Figure 3. Pd-catalyzed alkoxycarbonylation of 1,3-butadiene with meth-
anol: Variation of ligands.
is mainly formed, which afterwards rapidly is converted to the
desired adipate 4aa.
Next, we were interested to find out if this unexpected
solvent effect on 1,3-butadiene dicarbonylation is also ob-
served in the presence of other ligands. Hence, more than 20
standard mono- and bidentate phosphines were tested in this
industrially highly relevant process (Scheme S1); however,
only using ligands with the 1,2-bis(methyl)benzene backbone
gave substantial amounts of the targeted dicarbonylation
products. Thus, in case of the adamantly-substituted phos-
phine L5 also an increase of the product yield of 4aa with
decreasing methanol concentration is observed (Figure 3).
To understand the origin of this dramatic reactivity
difference depending on the methanol concentration a closer
look on the reaction mechanism is required. As shown in
Scheme 2, the reaction starts with the formation of the active
palladium hydride complex A,[14] which undergoes coordina-
tion and addition to 1,3-butadiene to give the thermodynami-
cally stable p-allyl palladium complex B. This complex might
be in equilibrium with the corresponding s-allyl species.[15]
After CO coordination and insertion to give C, nucleo-
philic attack by methanol leads to methyl 3-pentenoate 3.[16]
Preferably, this monocarbonylation product undergoes olefin
isomerization and a second carbonylation cycle (complexes
E,F) to give the desired dimethyl adipate.
catalyzed oxidative dicarbonylation of alkynes, a large excess
of water as co-solvent promoted the formation of maleic acid
with unprecedented catalytic efficiencies.[17] To understand
the specific influence of the methanol concentration on the
activity of certain catalysis in this overall process, several
control investigations were performed. As shown in
Scheme 3, in methanol as solvent the catalyst system with
L2 shows no conversion at all. This is also true for the
preformed palladium complex (Scheme 3a and b). This
observation makes clear that either the formation of the
palladium hydride or the reaction steps in cycle I are
prohibited by methanol. In agreement with this assumption
using the monocarbonylation product 3aa gave full conver-
sion in methanol as solvent and 4aa was obtained in 94%
yield (Scheme 3c). In contrast, using toluene as solvent under
identical conditions the alkoxycarbonylation of 1,3-butadiene
proceeded smoothly and 4aa was formed in 87% yield (97%
selectivity). As shown in Scheme 3d, only trace amounts of
the intermediate monocarbonylation product were observed.
Apparently, the Pd/dtbpx catalyst system allows for the two
carbonylation cycles in toluene, while in methanol only the
second cycle is working.
In general, the polarity and protic nature of the solvent
can influence the formation of the active hydride species and
each of the individual elementary steps in the two catalytic
cycles as well as the isomerization reactions.[16b,c] As an
example, Gabriele and co-workers discovered that, for Pd-
Next, we were interested in the generality of the observed
effects. Hence, the methoxycarbonylation of other 1,2- and
1,3-dienes to the corresponding diesters, which are of interest
for different fine and bulk chemical applications, was inves-
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tigated. More specifically, 37 different dienes and more than
30 alcohols were converted to the corresponding diesters in
good to very good yield (Figure 4). For example, linear 1,3-
dienes such as 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene,
1,3-octadiene showed excellent reactivity and regioselectivity.
Notably, the control reactions of 1,3-butadiene or isoprene in
pure methanol did not lead to any desired diesters under
otherwise identical reaction conditions.
Due to the fast isomerization reactions, substrates with
internal conjugated double bonds, for example, 1ag, 1am, 1an
also led preferentially to the respective terminal diester.
Apart from regular terminal or di-substituted olefins, also tri-
(1aq) and even tetra-substituted (1an) dienes with increased
steric hindrance on the carbon chain provided the linear
diesters 4aq and 4an in good yields and excellent selectivities.
Again, using 1aq in pure methanol showed the generalization
of the solvent influence and gave no tricarbonylation product
4aq. Furthermore, 1-aryl-substituted 1,3-dienes showed sim-
ilar performance. Here, excellent 1,4-site selectivity was
observed (4ar–4au) due to the stabilization of the benzylic
metal complex.
Interestingly, in addition to conjugated 1,3-dienes, a selec-
tion of seventeen 1,2-dienes including pure aliphatic and
aromatic derivatives were smoothly converted to the corre-
sponding linear diesters with similar activity and high
regioselectivity. Exemplarily, 1,2-butadiene and 1,2-penta-
diene gave the desired products in 73–74% yield (94–95%
regioselectivity), while no formation of the diester is observed
in methanol as solvent. Notably, this methodology also allows
the transformation of substrates with sensitive functional
groups such as B(OR)2.
Scheme 2. Catalytic cycles for the Pd-catalyzed alkoxycarbonylation of
1,3-butadiene with alcohol.
To assess the potential of the presented catalyst system for
practical applications, scale up experiments and a reaction
using dienic mixtures were performed (Figure 5). Gratify-
ingly, using 0.5 mol% of catalyst, dimethyl adipate was
obtained in 91% yield and 96% selectivity on > 150 g-scale.
In addition, a 1:1 mixture of 1,2- and 1,3-butadiene gave
dimethyl adipate in similar yield and selectivity.
Conclusion
In summary, we present the first Pd/dtbpx-catalyzed direct
dimethoxycarbonylation of 1,3-butadiene. Surprisingly, the
viability of this industrially relevant process is not only highly
dependent on the ligand and catalyst system, but also on the
methanol concentration. Using optimal conditions, this
straightforward transformation could be realized with ex-
cellent yield and selectivity for dimethyl adipate. The general-
ity of the presented catalyst system is demonstrated by the
efficient alkoxycarbonylation of 37 different 1,2- and 1,3-
dienes. Applying various alcohols provided a general ap-
proach to a variety of interesting diesters including function-
alized building blocks. The utility of the catalytic system is
also showcased by scale up experiments and reactions of
mixtures of dienes. We believe these findings will provide
motivation to better understand the critical role of solvents
and substrate concentration.
Scheme 3. Selected control experiments.
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Figure 4. Substrate scope for various dienes and alcohols. Yields are reported as isolated yields; the selectivity is the ratio of the linear diester to
branched diesters, which is determined by GC analysis.
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thank the analytical team of LIKAT for their kind support.
Funding from Evonik and the BMBF as well as the state
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access funding enabled and organized by Projekt DEAL.
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Conflict of interest
The authors declare no conflict of interest.
Keywords: adipates ·aliphatic diesters ·carbonylation ·
catalysis ·dienes
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Manuscript received: November 17, 2020
Revised manuscript received: January 8, 2021
Accepted manuscript online: January 15, 2021
Version of record online: March 3, 2021
Angew. Chem. Int. Ed. 2021, 60, 9527 –9533
ꢀ 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
www.angewandte.org
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