Telomerization of 1,3-butadiene with highly substituted alcohols using Pd/NHC-catalysts — Structure-reactivity-relationship of the O-nucleophile

Article abstract of DOI:10.1016/j.molcata.2016.05.002

Catalytic telomerization of 1,3-butadiene with alcohols is a catalytic reaction and an effective tool to synthesize 2,7-octadienyl ethers with different characteristics depending on the alcoholic substrate. While Pd/phosphine type catalysts were studied i

Full text of DOI:10.1016/j.molcata.2016.05.002

Accepted Manuscript
Title: Telomerization of 1,3-Butadiene with highly substituted
Alcohols Using Pd/NHC-Catalysts −
Structure-Reactivity-Relationship of the O-Nucleophile
Author: Thiemo A. Faßbach Robin Kirchmann Arno Behr
Steffen Romanski Dirk Leinweber Andreas J. Vorholt
PII:
S1381-1169(16)30173-X
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.molcata.2016.05.002
MOLCAA 9877
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Journal of Molecular Catalysis A: Chemical
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Accepted date:
14-4-2016
29-4-2016
2-5-2016
Please cite this article as: Thiemo A.Fassbach, Robin Kirchmann, Arno Behr, Steffen
Romanski, Dirk Leinweber, Andreas J.Vorholt, Telomerization of 1,3-Butadiene with
highly substituted Alcohols Using Pd/NHC-Catalysts minus Structure-Reactivity-
Relationship of the O-Nucleophile, Journal of Molecular Catalysis A: Chemical
http://dx.doi.org/10.1016/j.molcata.2016.05.002
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Telomerization of 1,3-Butadiene with highly substituted Alcohols
Using Pd/NHC-Catalysts – Structure-Reactivity-Relationship of the
O-Nucleophile
Thiemo A. Faßbacha, Robin Kirchmanna, Arno Behra, Steffen Romanskib, Dirk
Leinweberb, Andreas J. Vorholta,*
a Technische Universität Dortmund, Lehrstuhl für Technische Chemie, Emil-Figge-Str. 66, D-44227 Dortmund, Germany
b Clariant AG, D-65929 Frankfurt am Main, Germany
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Graphical abstract
Highlights
 A clear structure-reactivity-relationship regarding the employed alcohol
 Good yields of telomerization products from allylic alcohols
 First reported telomerization products from terpenols
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Abstract: Catalytic telomerization of 1,3-butadiene with alcohols is a
catalytic reaction and an effective tool to synthesize 2,7-octadienyl
ethers with different characteristics depending on the alcoholic
substrate. While Pd/phosphine type catalysts were studied in depth,
highly active Pd/NHC (=N-heterocyclic carbene) catalysts have been
studied in the telomerization almost exclusively along with methanol.
In the course of employing alcohols form renewables, e.g., lignin,
cellulose
or terpenes etc., a deeper understanding of the reactivity of these
catalysts is needed. In this work we present comprehensive
investigations with linear and
branched alcohols of different chain-lengths. Distinct tendencies in
reaction behavior between primary and secondary alcohols were found and
the lower reactivity of secondary alcohols could clearly be attributed
to electronic properties, along with steric hindrance.
Furthermore, the influence of double bonds in the alcohol chain has
been studied. Interestingly, alcohols with double bonds that are not
conjugated to the hydroxyl groups were shown to be more active than
saturated alcohols. Allylic alcohols however are significantly less
reactive than their saturated analog. With the gathered information we
were able to deduce a structurereactivity- relationship of certain
functional groups and substitution patterns. These findings were proved
by employing terpenols to gain new allylic terpenol ethers.
Keywords: Telomerization; Palladium; N-Heterocyclic Carbenes;
Homogeneous Catalysis; Renewables
1. Introduction
The dimerization of 1,3-dienes (e.g. 1,3-butadiene) along with an addition of a nucleophile is called a
telomerization (Scheme 1)[1]. It is mostly catalyzed by homogeneous palladium/phosphine
complexes, but also other metals like nickel[2] or platinum[3] have been reported to be active as
well. Since its discovery in 1966[4], the telomerization reaction was applied to a variety of
nucleophiles and dienes.
Regarding the diene substrate, there are only a few examples apart from 1,3-butadiene that have
been employed successfully. The most important one is isoprene[5–8], but dienes with longer chains,
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like 1,3-pentadiene and 1,3-hexadiene could also be converted[9,10]. To this date the largest
1,3-diene employed in a telomerization is -myrcene[11,12].
While the diene is limited to only a few compounds, there are many examples for different
nucleophiles used in this reaction. The most simple oxygen nucleophile is water, which can be
converted to octadienols, when 1,3-butadiene is applied. This reaction was realized as an industrial
process, which is run by Kuraray with an output of approximately 5,000 t/a[13]. The most important
nucleophiles are alcohols. From short, primary alcohols[14,15] over polyvalent alcohols like
glycols[16–18] or glycerol[19–21] to polyols like sugars[22–27], various catalytic systems with
different ligands have been engaged. On an even higher scale (> 100,000 t/a) the telomerization of
1,3-butadiene with methanol is run by Dow Chemicals in Tarragona, in order to finally produce
1-octene. Another type of widely used nucleophiles are amines[5,28], which often show higher
reaction rates than alcohols[29]. Apart from that, there are few more nucleophiles like CO2[30–32],
phenols[33–35] and acids[36] that have been employed.
In the last years, Beller et al. introduced N-heterocyclic carbene (NHC) ligands as a highly active
alternatives to the common phosphine ligands[37,38]. It was shown that these ligands are very
effective for telomerizations with alcohols and amines[39]. Especially the palladium precursor
Pd(IMes)(dvds) (= [(1,3-dimesitylimidazolin-2-ylidene)-Pd-ƞ2,ƞ2-1,1,3,3-tetramethyl-1,3-divinyl-
disiloxane]) (Scheme 2) is active at very low concentrations (down to 0.0003 mol%) and shows high
selectivities in the telomerization [40]. Furthermore, it is a commercially available compound, thus
studies regarding an industrial use are eligible.
It is known that the reactivity of the palladium/NHC catalysts strongly depends on the nature of the
nucleophile, meaning the type (e.g. O-nucleophile or N-nucleophile) and the substitution pattern of
the nucleophile[29]. While there are comprehensive studies on the influence of the nucleophile using
Pd/PR3-catalysts[15,41], there are no equivalent studies in which Pd/NHC catalysts have been
employed. However, the high activities with methanol and hints that these new catalysts are capable
of converting sterically and electronically more demanding alcohols make in-depth studies in this
field an attractive research goal. A comprehensive understanding of reactivities with various alcohols
could broaden the spectra of the telomerization. Thus, enabling new catalytic conversions of
renewable substrates, in this work the gained insights of the structure-reactivity-relationship were
transferred to terpenols using the highly active Pd/IMes catalyst.
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2. Experimental
2.1. Reagents
Chemicals were purchased from Acros Organics (Geel, Belgium), Sigma-Aldrich (Steinheim, Germany)
and TCI (Tokyo, Japan). 1,3-butadiene was obtained from Messer (Bad Soden, Germany).
All chemicals were employed without drying or any further purification. Catalyst Pd(IMes)(dvds) was
donated by Umicore (Brussels, Belgium).
2.2. Telomerization experiments
All reactions were performed in a 25 mL custom-made stainless steel autoclave[42]. The catalyst was
weighed directly into the reactor pot. Then the alcohol (50 mmol) was added gravimetrically, as well
as NaOH (0.5 mmol). The reactor was closed and 1,3-butadiene (100 mmol) was added volumetrically
via a pressure-resistant tube. To determine the accurate mass of the added 1,3-butadiene, the
reactor was weighed before and after addition. Afterwards the reactor was pressurized with 8 bar
argon and placed in a heated aluminum block at 80 °C. The reaction was magnetically stirred at
500 rpm. After 4 h the reaction was stopped using an ice-bath.
2.3. Product analysis
Routine gas chromatographic analyses were performed on an Agilent 7890B instrument (Santa Clara,
USA) equipped with a flame ionization detector (FID) and a HP-5 capillary column (30 m, diameter
0.32 mm, film thickness 0.25 µm) connected to an auto sampler (7693) and an injector (G4513A). GC-
MS analyses of the products were carried out on an Agilent 5977A MSD (70 eV). NMR spectra were
recorded on Bruker DRX spectrometers with TMS as internal standard. CDCl3 was used as solvent and
purchased from Deutero.
3. Results & Discussion
Inspired by the high activities of the catalytic system Pd/IMes and the capability of converting
alcohols to their respective octadienyl ethers, where the classical Pd/PR3 catalysts fail, we wanted to
evaluate the scope of the telomerization of 1,3-butadiene with alcohols systematically. With a clear
structure-reactivity-relationship at hand the feasibility of the telomerization with any alcohol was
assessable.
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The first investigations considered linear, primary alcohols, since they are the most active
O-nucleophiles.
3.1. Saturated Alcohols
3.1.1. Linear Alcohols
As shown in Table 1, the catalytic system Pd/IMes is compatible with linear, primary alcohols over a
wide range of chain length without significant changes to the activity or selectivity. The yield of the
telomers is about 70% – 75%, the dimer yields are about 15% - 20%. The reaction conditions should
demonstrate the reaction behavior well and were applied with a focus on high substrate
concentrations and catalyst loadings, leading to high space-time-yields. Therefore we applied
stoichiometric substrate ratios and low catalyst concentrations along with a base. The base is of great
importance for Pd/NHC catalysts to maintain high reaction rates. As Haumann et al. showed with
kinetic studies, the produced alkoxide reacts with a transition state in the catalytic cycle[43]. Higher
selectivities towards the telomerization product could be achieved by a significant excess of the
nucleophile.
Under these reaction conditions methanol is less active than the alcohols with longer chains. In this
context Cavell et al. suggested a stabilization of the catalyst by longer carbon chains[9]. Another
reason that should be discussed at this point is the nucleophilicity of the respective alkoxide.
Methanol is the strongest acid among the tested alcohols, its nucleophilicity is therefore the lowest.
Disregarding any steric considerations, this could be the reason for the slightly lower activity
compared to the other linear, primary alcohols. Every primary, linear alcohol longer than methanol
leads to equal results over a long range of chain lengths, which is a striking advantage compared to
phosphine ligands. The catalysts with triphenylphosphine ligands suffer from a severe loss of
selectivity with increasing chain lengths of the alcohols, yielding large quantities of dimers. The TON
of the Pd/PPh3-catalyst decreases below 2000 with alcohols longer than C5, where the selectivity
towards the telomers is only about 60%[14]. A higher selectivity with higher alcohols were only
achieved with more basic phosphines, e.g. triethylphosphine, like Patrini showed[41]. In the case of
n-octanol for example, they reported high conversions and selectivities towards the telomers,
resulting in TONs up to 1,800. With the Pd/IMes catalyst a tenfold of these TONs are reachable (Table
1). Linear alcohols are obviously highly active compounds in the Pd/IMes catalyzed telomerization,
but only if the hydroxyl group is located at the end of the carbon chain. The corresponding secondary
alcohols are much less reactive. Not only is the formation of telomers reduced, but also the
conversion of 1,3-butadiene in general. In the case of the employed pentanols, the conversion
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decreases from 92% with 1-pentanol over 38% (2-pentanol) to 25% (3-pentanol). This drastic decline
raises the question, which influence plays the most important role in the catalytic cycle. There are
either electronic properties that inhibit the catalytic conversion or the decrease takes place only for
sterical reasons.
3.1.2. Cyclic alcohols
We have shown that secondary alcohols suffer from a much lower activity in the telomerization than
their primary equivalent. For many renewable substrates offer secondary alcohols, it is important to
determine, whether these hydroxyl groups can be converted with this catalytic system. In order to
separate the steric from the electronic influence, we employed the corresponding cyclic alcohols
(Table 2) and compared the results with the ones shown in Table 1.
The results show that cyclic alcohols are more reactive than the secondary, linear ones with the same
chain length. For example cyclo-pentanol yields 48% of the telomerization product, which is twice as
much as with 2- and 3-pentanol. Again, it can be stated, that the Pd/IMes-catalyst is much more
versatile than Pd/PPh3, as there is no formation of telomers in the telomerization of 1,3-butadiene
with e.g. cyclohexanol at all using these catalysts[15].
Due to the nearly identical electronic properties of the hydroxyl function in cyclo- and 2- or
3-pentanol, this increase can be attributed to the lower steric demand. This is also consistent with
the decrease in activity with larger rings of the cyclo-alcohols. We already showed that the longer
chain itself does not interfere with the reaction, but since the bond angle for larger cycles increase,
the steric demand does as well.
We could successfully increase the yield of telomers by decreasing the steric demand of the
secondary alcohol, using cyclo-pentanol. Still, the primary analog 1-pentanol yields significantly more
products. We therefore suggest that there are electronic reasons for the higher activity of primary
than of secondary alcohols in the Pd/IMes catalyzed telomerization.
There are many renewable, primary alcohols, like terpenols, bearing non-linear alcohol moieties. The
activity of primary alcohols benefits from electronic reasons rather than from sterical ones, we
therefore wanted to find the sterical limits of this reaction.
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3.1.3. Branched alcohols
Since the electronic properties of the employed alcohols are obviously as important as the steric
hindrance, we wanted to know how far this concept can be generalized. Therefore primary alcohols
with bulkier alkyl chains were used (Table 3).
Obviously an iso-branch has little to no influence on neither the conversion nor the selectivity in the
telomerization. In both cases, iso-pentanol and iso-butanol, the reactivity did not change significantly
compared to the linear alcohol.
Surprisingly, even the sterically very demanding neo-pentanol could be successfully converted into
the corresponding ether with comparably good yields of 57%. This value exceeds the product yields
reached with any secondary pentanol employed in this study. This substantiates the finding that the
steric influence is not as important to the reactivity, as the electronic properties of the alcohol
moiety.
3.2. Unsaturated alcohols
3.2.1. Alkenols
Many natural occurring alcohols have unsaturated backbones, e.g. terpenols. Regarding the
importance of electronic properties of the alcohol in the Pd/IMes catalyzed telomerization, it is of
great interest to examine the reaction behavior of unsaturated alcohols. It has to be said that a
double bond within an alcohol structure changes both, the electronic and the steric attributes of the
substrate. At first, we carried out reactions with alcohols containing a double bond, but not an allylic
hydroxyl group (Table 4) and compared the results to the saturated analogs.
5-Hexen-1-ol was found to be converted almost completely, while only 82% of the desired product
was yielded. The reason for this is the palladium catalyzed isomerization of the unsaturated alcohol
to the aldehyde, followed by an aldol condensation. The aldol condensation product was identified
via GC-MS and it yield was about 10%. It is known that linear, unsaturated alcohols can undergo an
isomerization with palladium catalysts and that unsaturated alcohols with substituted double bonds
are more stable under these conditions. Therefore isoprenol (3-methylbut-3-en-1-ol) was employed,
which led to higher product yields, as expected.
These two results show that unsaturated alcohols in general are more active in the Pd/IMes
catalyzed telomerization of 1,3-butadiene than saturated ones. At first glance, higher electron
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density increases repulsion with the palladium-allyl-complex, and should therefore inhibit
approximation of the nucleophile.
3.2.2. Allylic alcohols
To clarify the influence of double bonds in the alcohol during the telomerization, we tested allylic
alcohols and compared the results to the corresponding saturated alcohols (Table 5).
The telomerization of allylic alcohols was only described by Beger and Reichel in 1973 with Pd/PPh3
catalysts, yielding small amounts of 10% of the telomerization product[15]. This is equivalent to a
TON of only 200. Especially the telomer of 1,3-butadiene with allyl alcohol could be an interesting
building block for polymers, being an ,-unsaturated ether.
The chosen catalytic system leads to significantly higher yields, than the before mentioned Pd/P
catalysts. While the yield could be doubled, the TON multiplies by 24. The NHC ligand obviously
enables the telomerization of unsaturated alcohols much more than the classical Pd/PR3 catalysts do.
But the product yields are still significantly lower, compared to those with the saturated alcohols
(Table 1). The allylic alcohols are less reactive, which could be explained by the higher electron
density due to the double bond next to the hydroxyl group. This potentially hinders the approach of
the alkoxylate to the catalyst. Remarkably, we found no aldol condensation products of the
conjugated aldehyde of the allylic alcohols, unlike with 5-hexen-1-ol.
We put the gathered information of the employed model substrates in a “substrate map” giving a
semi-quantitative overview, how alcohols react in the Pd/NHC catalyzed telomerization (Scheme 4).
3.2.3. Terpenols
With the gained insights to telomerization reactions with unsaturated alcohols at hand we employed
renewable alcohols with the molecule patterns from the model substrates, like terpenols in our
reactions (Scheme 5).
The non-allylic alcohol citronellol yields more than twice as much product, as the allylic alcohol nerol
(Table 6). These results are in accordance with the results from allylic alcohol and crotyl alcohol and
their respective saturated analogs. Allylic alcohols are generally less reactive in the telomerization
reaction.
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The secondary, long chain alcohol methyl ricinoleate could not be converted to its respective
octadienyl ether, neither were any 1,3-butadiene dimers formed. These results show that the aligned
structure-reactivity-relationship is valid for the employed renewable nucleophiles.
4. Conclusions
In the presented work we examined the possibilities of the palladium/NHC catalyzed telomerization
of 1,3-butadiene with higher substituted alcohols. Using the popular IMes ligand, we achieved
constant high yields of primary, linear alcohols of about 75% up to a chain length of eight. This is a
noticeably improvement compared to the Pd/PR3 catalysts. When secondary alcohols are employed,
the trend of decreasing yields matches the trend with phosphine ligands, still the overall yields and
TONs are significantly higher with the IMes ligand. To distinguish between electronic influences of
secondary hydroxyl groups and the steric hindrance, we employed cyclic alcohols. The sterical
advantage over non-cyclic secondary alcohols resulted in higher yields (YTelo = 48% for cyclo-
pentanol), but not to the extent of primary alcohols (YTelo = 75% for 1-pentanol). To determine the
influence of steric hindrance, we then applied primary alcohols with very bulky alkyl moieties.
Interestingly, even the sterically challenging neo-pentanol was converted to its octadienyl ether with
a yield of 57%, exceeding the product yield of any secondary alcohol employed in this work.
A double bond within the alkyl chain of an alcohol does not interfere with the telomerization
reaction, but yet increases reactivity, compared to the saturated analogs. However, if the double
bond forms an allylic alcohol, the reaction suffers from a severe loss of activity. This behavior could
be demonstrated on short chain alcohols, like allyl alcohol vs. 1-propanol (24% vs. 72% yield of
telomers).
We were able to prove the reaction behavior to certain functional groups and substitution patterns.
With the gained structure-reactivity-relationship, we were able to estimate the reactivity of
renewable nucleophiles, like terpenols. To the best of our knowledge, this is the first example of a
telomerization with terpenols, allylic and non-allylic ones, yielding terpene-derived (di-)allylic ethers.
Acknowledgements
The financial support from Clariant AG is gratefully acknowledged.
The authors thank Umicore AG & Co. KG for the donation of the Pd-NHC precursors.
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Appendix A. Supplementary Data
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Scheme 1: Telomerization of 1,3-butadiene with an alcohol
- 16 -

Scheme 2: The Pd(IMes)(dvds) precursor
- 17 -

Scheme 3: Telomerization of 1,3-butadiene with allylic alcohols, yielding diallylic ethers
- 18 -

Scheme 4: "substrate map" of the Pd/IMes catalyzed telomerization with different alcohols
- 19 -

Scheme 5: Telomerization of 1,3-butadiene with nerol
- 20 -

Table 1: Telomerization experiments with primary and secondary linear alcohols
TON
Alcohol
Xbutadiene
Stelomers
Sdimers
[mol/mol]
16,200
18,200
17,800
6,200
C1
C1
Methanol
Ethanol
81
91
89
31
94
92
38
25
92
94
78
81
81
84
79
82
47
72
79
81
22
19
19
16
21
18
53
28
21
19
1-Propanol
2-Propanol
1-Butanol
1-Pentanol
2-Pentanol
3-Pentanol
1-Hexanol
1-Octanol
C3
C4
18,800
18,400
7,600
C5
5,000
18,400
18,800
> C5
Conditions:
0.005 mol% Pd(IMes)(dvds) based on 1,3-butadiene, 1 mol% NaOH based on the alcohol,
n(1,3-butadiene):n(alcohol) = 2:1, T = 80 °C, t = 4 h, 500 rpm.
X and S in % based on 1,3-butadiene. TONs are calculated as converted moles of
1,3-butadiene per employed mol palladium. Results determined by GC-FID.
- 21 -

Table 2: Telomerization experiments with cyclic alcohols
TON
Alcohol
Xbutadiene
Stelomers
Sdimers
[mol/mol]
13,400
14,000
5,200
cyclo-Pentanol
cyclo-Hexanol
cyclo-Octanol
67
57
26
72
61
73
28
49
27
Conditions:
0.005 mol% Pd(IMes)(dvds) based on 1,3-butadiene, 1 mol% NaOH based on the alcohol,
n(1,3-butadiene):n(alcohol) = 2:1, T = 80 °C, t = 4 h, 500 rpm.
X and S in % based on 1,3-butadiene. TONs are calculated as converted moles of
1,3-butadiene per employed mol palladium. Results determined by GC-FID.
- 22 -

Table 3: Results with primary alcohols with varying bulky rests
Alcohol
Xbutadiene
TON
Stelomers
Sdimers
92
18,400
84
16
iso-Butanol
87
80
55
17,400
16,000
11,000
88
71
84
12
29
16
iso-Pentanol
neo-Pentanol
neo-Hexanol
Conditions:
0.005 mol% Pd(IMes)(dvds) based on 1,3-butadiene, 1 mol% NaOH based on the alcohol,
n(1,3-butadiene):n(alcohol) = 2:1, T = 80 °C, t = 4 h, 500 rpm.
X and S in % based on 1,3-butadiene. TONs are calculated as converted moles of
1,3-butadiene per employed mol palladium. Results determined by GC-FID.
- 23 -

Table 4: Results with unsaturated alcohols
Alcohol
Xbutadiene
TON
Stelomers
Sdimers
90
18,000
91
9
5-Hexen-1-ola)
>99
>19,800
86
14
Isoprenol
Conditions:
0.005 mol% Pd(IMes)(dvds) based on 1,3-butadiene, 1 mol% NaOH based on the alcohol,
n(1,3-butadiene):n(alcohol) = 2:1, T = 80 °C, t = 4 h, 500 rpm.
X and S in % based on 1,3-butadiene. TONs are calculated as converted moles of
1,3-butadiene per employed mol palladium. Results determined by GC-FID.
a): 10% aldol condensation product of 1-hexanal was detected.
- 24 -

Table 5: Results with allylic alcohols
Alcohol
Xbutadiene
TON
Stelomers
Sdimers
24
4,800
92
8
Allyl Alcohol
Crotyl Alcohol
32
6,400
88
12
Conditions:
0.005 mol% Pd(IMes)(dvds) based on 1,3-butadiene, 1 mol% NaOH based on the alcohol,
n(1,3-butadiene):n(alcohol) = 2:1, T = 80 °C, t = 4 h, 500 rpm.
X and S in % based on 1,3-butadiene. TONs are calculated as converted moles of
1,3-butadiene per employed mol palladium. Results determined by GC-FID.
- 25 -

Table 6: Telomerizations with renewable nucleophiles
Alcohol
Nerol
Xbutadiene
TON
Stelomers
Sdimers
27
5,400
81
19
62
12,400
90
10
Citronellol
-
-
-
-
Methyl Ricinoleate
Conditions:
0.005 mol% Pd(IMes)(dvds) based on 1,3-butadiene, 1 mol% NaOH based on the alcohol,
n(1,3-butadiene):n(alcohol) = 2:1, T = 80 °C, t = 4 h, 500 rpm.
X and S in % based on 1,3-butadiene. TONs are calculated as converted moles of
1,3-butadiene per employed mol palladium. Results determined by GC-FID.
- 26 -