Tandem Reductive Hydroformylation of Castor Oil Derived Substrates and Catalyst Recycling by Selective Product Crystallization

Article abstract of DOI:10.1002/cctc.201700965

An orthogonal tandem catalytic system consisting of rhodium and ruthenium complexes yielded linear C₁₂ α,ω-bifunctional compounds from commercial, castor oil derived renewable substrates. With aldehyde yields up to 88 % and selectivities to the linear species of up to 95 %, this approach is direct and atom economic and provides easy access to potential polymer precursors for polycondensates. Additionally, a straightforward method for selective product crystallization was developed, which enabled recycling of the tandem catalytic system for two runs with excellent activity and simultaneously provided a high-purity product.

Full text of DOI:10.1002/cctc.201700965

Accepted Article
Title: Tandem Reductive Hydroformylation of Castor Oil Derived
Substrates and Catalyst Recycling by Selective Product
Crystallisation
Authors: Marc Furst, Vedat Korkmaz, Tom Gaide, Thomas
Seidensticker, Behr Arno, and Andreas Vorholt
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: ChemCatChem 10.1002/cctc.201700965
Link to VoR: http://dx.doi.org/10.1002/cctc.201700965
A Journal of
www.chemcatchem.org

10.1002/cctc.201700965
ChemCatChem
COMMUNICATION
Tandem Reductive Hydroformylation of Castor Oil Derived
Substrates and Catalyst Recycling by Selective Product
Crystallisation
M. R. L. Furst,[a] V. Korkmaz,[a] T. Gaide,[a] T. Seidensticker,[a] A.Behr[a] and A. J. Vorholt*,[a]
tBu
tBu
tBu
Abstract: An orthogonal tandem catalytic system consisting of
rhodium and ruthenium complexes yields linear C12 α,ω-bifunctional
compounds from commercial, castor oil derived renewable
substrates. With aldehyde yields up to 88% and selectivities to the
linear species of up to 95%, this approach is a direct, atom-
economic and easy access to potential polymer precursors for
polycondensates. Additionally, a straightforward method for selective
product crystallisation has been developed, enabling the recycling of
the tandem catalytic system for two runs with excellent activity and
simultaneously providing a high purity product.
O
O
Ph
Ph
H
Ph
Ph
Ph
Ph
Ph
CO
CO
Ru
Ph
OC
Ru
tBu
(RO)2
R=1-naphthyl,
H
O
O
CO
P
P(OR)2
A4N3
catalyst
Shvo's
MeO
OMe
The addition of syngas (CO/H2 mixture) to double bonds under
aldehyde formation is generally referred to as hydroformylation.
It is one of the most important applications of homogeneous
transition metal catalysis in the chemical industry, producing
more than 12 million metric tons of aldehydes per year.[1]
Especially the n-selective hydroformylation of terminal alkenes is
of high interest since the resulting aldehydes can be converted
into the corresponding linear n-alcohols, which are of high value.
The transformation of alkenes to n-alcohols via hydroformylation
can in principle be done by two different approaches:
tBu
tBu
O
O
O
P
P
O
O
PPh2
PPh2
O
O
Xantphos
Biphephos
Figure 1. Shvo’s catalyst and applied ligands in the n-selective reductive
hydroformylation
•
A multistep process consisting of alkene hydroformylation,
aldehyde purification, aldehyde reduction and alcohol
purification[2]
the corresponding n-alcohols.[8,9] A similar tandem catalytic
system consisting of a Rh/Sulfoxantphos catalyst on supported
ionic liquid phase in combination with Shvo’s catalyst on SiO2 for
butanol synthesis from propene was reported by Bell et al.[10]
Based on their previously reported system, Nozaki et al. were
even able to extend their tandem catalytic system by preceding
isomerization yielding linear alcohols from internal olefins by
changing the ligand to A4N3 (Figure 1) and adding additional
Ru3(CO)12.[11] Thus, they yielded 53% linear methyl
19-hydroxynonadecanoate starting from methyl oleate using the
catalyst system described above. The application of unsaturated
fatty acid methyl esters (FAMEs) is particularly beneficial since
the resulting linear bifunctional molecules are interesting AB-
type monomers for polycondensates.
In this regard, the readily available and from castor oil renewably
derived substrates methyl 10-undecenoate (1a), 10-undecenol
(1b) and 10-undecenoic acid (1c) are further very potential
starting materials for the production of monomers. For instance,
1a is already industrially utilized for the production of polyamide-
11 (Rilsan®),[12] and also other promising approaches have been
reported.[13] However, reductive hydroformylation has not been
presented so far and would thus considerably broaden the
spectrum. Via the corresponding intermediate linear aldehydes
2a-c, the resulting linear bifunctional alcohols 3a-c have very
high potential as monomers for polycondensates (e.g. polyester
12, Figure 2).
•
A
tandem reaction consisting of concurrent alkene
hydroformylation and aldehyde reduction in one pot (i.e.
reductive hydroformylation) followed by alcohol purification.
The tandem reaction approach obviously is a very attractive
alternative since energy intensive intermediate aldehyde
purification is unnecessary.[3] Consequently, many attempts can
be found in the literature to realize this reaction sequence in an
auto-tandem catalytic system applying Co,[4] Rh,[5] Pd[6] or Ru[7,8]
as the only catalyst metal in combination with different nitrogen
or phosphorus ligands.
Another efficient approach to realize this tandem reaction is the
use of two orthogonal catalysts, one for hydroformylation and
one for the reduction of aldehydes. Nozaki et al. reported about
an orthogonal tandem reaction consisting of Rh/Xantphos
hydroformylation catalyst and Shvo’s catalyst (Figure 1) for
aldehyde reduction enabling high yields and selectivity towards
[a]
Dr. Marc R. L. Furst, Vedat Korkmaz, Tom Gaide, Dr. Thomas
Seidensticker, Prof. Dr. Arno Behr, Dr. Andreas J. Vorholt
Chair for Industrial Chemistry, Faculty for Biochemical and Chemical
Engineering
Technical University (TU) Dortmund
Emil-Figge-Straße 66, 44227 Dortmund/Germany.
E-mail: Andreas.vorholt@bci.tu-dortmund.de
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/cctc.201700965
ChemCatChem
COMMUNICATION
e.g.
Polyester-12
Polyester-12,X
Castor Oil
100
80
60
40
20
0
100
80
60
40
20
0
work
this
A
C
O
R
OH
R
R
4
4
4
R=
R= CH
R=
1a
1b
1c
2a-c
3a-c
COOMe methyl 10-undecenoate
2OH 10-undecenol
COOH 10-undecenoic acid
(
(
(
)
)
)
0
30
60
90
120
150
180
0
10
20
30
40
50
Time (min.)
Time (min.)
100
80
60
40
20
0
100
80
60
40
20
0
Figure 2. Reductive hydroformylation of castor oil derived substrates 1a-c for
the synthesis of linear bifunctional alcohols 3a-c via the intermediate linear
aldehydes 2a-c.
B
D
Despite the high potential of transition metal catalysed tandem
reactions for the synthesis of polyester monomers from oleo
chemicals, their application is still highly limited. This in our
opinion is mainly due to two major concerns in the downstream
process:
0
30
60
90
120
150
180
0
10
20
30
40
50
Time (min.)
Time (min.)
•
•
the required high purity of the monomer
a considerable lack of efficient catalyst recycling concepts
(particularly for orthogonal tandem reaction systems)
Figure 3. Yield vs. time: Reduction of aldehyde 2a to alcohol 3a (with ex situ
Shvo’s catalyst (A) and in situ reduction system (B)); Reductive
hydroformylation of 1a to alcohol 3a (with ex situ Shvo’s catalyst (C) and in
situ reduction system (D)).
□ methyl 10-undecenoate 1a
• methyl 12-oxododecanoate 2a
▶ methyl 12-hydroxydodecanoate 3a
Ensuring high purity of the product is a prerequisite for the
subsequent polycondensation reaction in order to gain
substantial molecular weights of the corresponding polymer.14
Recycling of catalysts is crucial for an economically feasible
process since rhodium and ruthenium are very expensive noble
metals and also the applied precursors and ligands are tailored
and, for that reason, expensive.
Conditions: for A: n2a = 22.2 mmol, 1 mol% Shvo’s catalyst, 100 mL toluene,
p(H2) = 10 bar, T = 150°C;
for
B:
n2a
=
22.2 mmol,
0.33 mol%
Ru3CO12
,
1 mol%
tetraphenylcylopentadienone, 100 mL toluene, p(H2) = 10 bar, T = 150°C;
for C: n1a = 22.2 mmol, 1 mol% [Rh(CO)2acac], 2 mol% Biphephos, 1 mol%
Shvo’s catalyst, 100 mL toluene, p(CO/H2) = 20 bar, T = 150°C;
We envisaged tackling both of these challenges concurrently, by
developing a selective product crystallisation procedure for
simultaneous catalyst recycling and product purification.
Additionally, the crystallisation approach represents a rather mild
method and is therefore less energy-intensive, of high interest
and possesses high future potential.[15]
For doing so, we initially tackled the combination of the
Rh/Biphephos system for highly n-selective hydroformylation
and Shvo’s Ru catalyst system for aldehyde reduction. We
chose methyl 10-undecenoate (1a) as the model substrate for
first experiments. Initially, hydroformylation of 1a for the
production of 2a with the Rh/Biphephos system turned out to be
straightforward as expected, with 99% conversion after one hour
and a selectivity of >98% for the linear aldehyde (see SI for
details and conditions). Only negligible amounts of alcohol 3a
for D: n1a = 22.2 mmol, 1 mol% [Rh(CO)2acac], 2 mol% Biphephos, 0.33 mol%
Ru3CO12, 1 mol% tetraphenylcylopentadienone, 100 mL toluene, p(CO/H2) =
20 bar, T = 150°C. Detailed experimentals: see SI.
under the chosen conditions, but extensive double bond
hydrogenation and isomerization have been observed.
To compare the activity in aldehyde reduction between the two
systems (commercial ex situ vs. in situ system), we first
performed conversion vs. time plots (Figure 3) in the
transformation of 2a into 3a under hydrogen pressure. We
noticed that the reduction of the aldehyde 2a is straightforward
and leads to full conversion to the desired linear alcohol 3a with
either system (Figure 3, graphs A and B). However, an induction
period does exist using the in situ built catalyst (B), which was
expected and is not detrimental to the reaction outcome.
were detected without the aid of
a reduction catalyst.
Motivated by this fact, the tandem reductive hydroformylation of
1a to the linear alcohol 3a via the intermediate aldehyde 2a was
tested. Applying the Rh/Biphephos system for hydroformylation
leads to a similar conversion path to the desired product 3a,
whatever the reduction system is used (Figure 3, in situ (graph
C) or ex situ (graph D)). Once again, an induction period
appears for the in situ built reduction system. For both systems,
Additionally, neither Shvo’s catalyst nor a combination of
Ru3CO12/Biphephos showed hydroformylation activity under
these conditions, in accordance with reports by Nozaki et al.
before.[8,9]
In ongoing studies on the single step formation of the alcohol 3a
by reduction of 2a, we discovered, to our surprise, the possibility
of generating an active aldehyde reduction system in situ by
applying Ru3CO12 and tetracyclone (2,3,4,5-Tetraphenyl-2,4-
cyclopentadien-1-one). In situ generation of the reduction
catalyst is of high value from an economic and ecologic
perspective, since it saves additional time, effort and auxiliary
chemicals in catalyst synthesis and the catalyst precursors are
much cheaper compared to e.g. Shvo’s catalyst.
full conversion was achieved after 18
h with excellent
selectivities. Additionally, fast isomerization of the terminal
double bond of 1a into an isomeric alkene mixture has been
observed. However, only the terminal double bond has been
hydroformylated with very high selectivity with the chosen
Rh/Biphephos system, as already described in literature.[16] The
main undesired reactions were the production of branched
aldehydes (2a,branched) from internal alkenes, leading to branched
The application of Ru3CO12 alone or in combination with
Biphephos did not lead to an active aldehyde reduction system
This article is protected by copyright. All rights reserved.

10.1002/cctc.201700965
ChemCatChem
COMMUNICATION
alcohols (3a,branched), and the hydrogenation of methyl 10-
undecenoate (1a) to methyl undecanoate.
8
6
4
2
0
100
80
60
40
20
This series of experiments confirms the feasibility, and moreover,
the performances of an in situ built aldehyde reduction system
comparable to Shvo’s catalyst in reductive hydroformylation for
the first time. Although the unequivocal evidence for the in situ
formation of Shvo’s catalyst has not been attempted yet, the
similar catalytic activity is a strong hint in that direction.
With these first insights in hand, we modified the reaction
conditions for the reductive hydroformylation in order to speed
up the reaction sequence and to produce more alcohol product
per time. Increasing the amount of catalyst and substrate
applied, the reaction time for reaching full conversion could be
decreased to one hour, by maintaining high selectivity (Table 1,
Entry 1). Moreover, in our effort to provide a greener alternative
to toluene, isopropanol worked out very well as a recommended
solvent according to CHEM21 solvent guide.[17]
0
1
2
3
Amount of 3a (g)
Conversion of 1a (%)
Figure 1. 1: first reaction; 2: first recycling; 3: second recycling.
Conditions: Isopropanol 30 mL, 5 mL 1a (22.2 mmol), 1 mol% [Rh(CO)2acac],
2 mol%
Biphephos,
0.33 mol%
Ru3(CO)12
,
1 mol%
The developed orthogonal tandem catalytic [Rh]/[Ru] system
proved to tolerate also alcohols and a free carboxylic group by
maintaining similar activity and regioselectivity (Table 1). Under
the optimized reaction conditions, substrates 1b and 1c were
also smoothly transformed into the corresponding alcohol
products with 73% and 78% yield and a linear selectivity of 91%
and 95%, respectively. However, substrate 1b gave comparably
higher yields for the saturated substrate undecanol of 22%. This
is caused by the isomerization of the double bond to the other
terminus of the molecule into the vinyl position of the alcohol
function. This intermediate tautomerizes to the intermediate
undecanal, which is effectively reduced by the present Ru
catalyst system. Hence, the higher yield of saturated substrate
product for this specific substrate is rather an instance of high
aldehyde reduction potential in the tandem system than a lack of
chemoselectivity.
tetraphenylcylopentadienone, T = 150°C, t = 1 h.
We developed the following working principle: the crude reaction
mixture is transferred from the cooled autoclave into a double-
jacketed crystalliser equipped with a frit at the bottom. It is
cooled down at a certain rate below a temperature at which the
product crystallises. Through vacuum filtration, the liquid,
catalyst containing reaction mixture is isolated and separated
from the solid product, and the latter is analysed by GC-FID for
determining its purity and by ICP-OES for residual metals’
content.
In an initial experiment, after reductive hydroformylation of 1a at
standard conditions, the reaction mixture was cooled down in
the crystalliser at a rate of 2 K per hour (see SI for details).
Using this simple method allowed us to obtain large crystals: the
filtration was straightforward and quick. The purity of the
crystalline linear alcohol 3a was >97% and ICP analysis
provided a leaching of 0.72 mg of Rh and 1.59 mg of Ru (3.3%
and 3.0% of initial metal content, respectively).
Next, the recycling of the Rh/Ru orthogonal catalyst system by
developing
a
temperature induced selective product
crystallisation was tackled. For that, we chose ester alcohol
product 3a as the model substrate.
The catalyst leaching with this non-optimized method is
comparable to other recycling strategies for homogeneous
transition metal catalysts like thermomorphic multicomponent
solvent systems (TMS)[18] or organic solvent nanofiltration,[19]
Table
1 Reductive hydroformylation of 1a-c under optimized reaction
conditions
making selective product crystallisation
significant future potential.
a
strategy with
The high product purity of 3a already after the first run in
combination with the low leaching values motivated us to tackle
the recycling of the orthogonal tandem catalytic system next.
After a second experiment, the cooling process in the crystalliser
was set to a decrease in temperature from room temperature to
-20°C, letting the product crystallise from the mixture. After
vacuum filtration, the liquid filtrate containing the catalysts, the
solvent and possible side-products was replenished with the
fresh substrate (1a). It was introduced via cannula back to the
autoclave, which was pressurized once again with syngas and
warmed up to 150°C for one hour. Using this methodology, the
orthogonal tandem systems could be successfully reused for
three times without a significant loss in activity and selectivity
(Figure 4). While GC-FID conversion of the substrate 1a was
constant, the isolated yield of the desired product after each
recycling increased. This phenomenon is due to the fact only
Y hydr.
l/b
X1a-c
[%]
Y2a-c,br. Y2a-c
Y3a-c,br. Y3a-c
Substrate
in alcohol
products
Substrate
[%]
[%]
[%]
[%]
[%]
1a
1b
98
99
95
7
22
2
1
2
7
2
2
8
6
6
4
82
67
74
93:7
91:9
95:5
1c[a]
Conditions: Isopropanol 30 mL, 5 mL 1a-c (22.2 mmol), 1 mol%
[Rh(CO)2acac], 2 mol% Biphephos, 0.33 mol% Ru3(CO)12 1 mol%
tetraphenylcylopentadienone), p(CO/H2) 40 bar, 150°C, 1 h.
,
=
T
=
t =
Conversion (X) and yields (Y) determined by GC-FID with external standard.
[a] Analysed as the corresponding methyl esters after methanolysis of the
crude reaction mixture.
This article is protected by copyright. All rights reserved.

10.1002/cctc.201700965
ChemCatChem
COMMUNICATION
C. Crause, L. Bennie, L. Damoense, C. L. Dwyer, C. Grove, N.
Grimmer, W. J. van Rensburg, M. M. Kirk, K. M. Mokheseng, S. Otto
and P. J. Steynberg, Dalton Trans, 2003, 2036–2042; d) P. N. Bungu
and S. Otto, Dalton Trans., 2007, 2876–2884; e) D. Wu, Y. Wang, G. Li,
J. Jiang and Z. Jin, Cat. Commun., 2014, 44, 54–56.
48% of the desired product 3a can be recovered after the first
crystallisation, and hence the remaining product accumulates in
the crude mixture after each recycling. However, this effect
shows that recycling of the product and intermediates does not
impede activity, nor have side-products been detected, which
potentially could result from consecutive reactions such as
acetals etc. Additionally, recycling of the product even enhances
crystallisation yield, virtually giving a 74% yield for the first
recycling and a 129% yield for the following one.
A third recycling, however, showed the system to lose its ability
to reduce the intermediate aldehydes to the corresponding
alcohols, and additionally, selectivity in hydroformylation to the
linear aldehyde decreased. This is presumably due to the loss of
ligands upon recycling, leading to decreased Ru/tetrayclone
ratio, not being suitable for in situ reduction of more non-linear
aldehydes.
In conclusion, we proved the high potential of catalyst recycling
through the mild method of selective product crystallisation.
Moreover, this method allowed us to recycle an orthogonal
tandem catalytic system for the first time which consists of two in
situ built catalytic species, increasing simultaneously the interest
of this challenging orthogonal tandem reaction. The tandem-
reaction based system simplifies the procedure of converting
natural feedstocks into a high-potential polymer precursor.
However, the intrinsic limitation of this approach, i.e.
accumulation of side-products by their recycling with the catalyst
phase represents a major challenge. Possible ways to overcome
this problem would be e.g. the combination with other separation
approaches such as extraction, potentially as a hybrid-technique.
The crystallisation/recycling procedure is currently tested for
other substrates and being optimized in order to amplify the
number of recycling cycles, lessening the metal leaching and
obtaining polymer grade products. Additionally, investigations on
the practical in situ generated aldehyde reduction system are
currently underway, in order to identify its exact nature.
[5]
J. K. MacDougall and D. J. Cole-Hamilton, J. Chem. Soc., Chem.
Commun., 1990, 165; b) J.-A. M. Andersen and A. W. S. Currie, Chem.
Commun., 1996, 1543; c) M. C. Simpson, A. W. S. Currie, J.-A. M.
Andersen, D. J. Cole-Hamilton and M. J. Green, Dalton Trans., 1996,
1793; d) L. Ropartz, R. E. Morris, D. F. Foster and D. J. Cole-Hamilton,
J. Mol. Cat. A, 2002, 182-183, 99–105; e) T. Ichihara, K. Nakano, M.
Katayama and K. Nozaki, Chem. Asian J., 2008, 3, 1722–1728; f) I. I. F.
Boogaerts, D. F. S. White and D. J. Cole-Hamilton, Chem Commun.,
2010, 46, 2194–2196; g) L. L. W. Cheung, G. Vasapollo and H. Alper,
Adv. Synth. Catal., 2012, 354, 2019–2022; h) B. A. Rodriguez and W. J.
Tenn, Appl. Catal. A: General, 2012, 421-422, 161–163; i) O. Diebolt, C.
Müller and D. Vogt, Catal. Sci. Technol., 2012, 2, 773-777.
[6]
[7]
D. Konya, K. Q. Almeida Leñero and E. Drent, Organometallics, 2006,
25, 3166–3174.
a) E. M. Gordon and R. Eisenberg, J. Organomet. Chem., 1986, 306,
C53-C57; b) J. F. Knifton, J. Mol. Cat., 1987, 43, 65–77; c) L. Alvila, T.
A. Pakkanen and O. Krause, J. Mol. Cat., 1993, 84, 145–156; d) L.
Alvila, J. Pursiainen, J. Kiviaho, T. A. Pakkanen and O. Krause, J. Mol.
Cat., 1994, 91, 335–342; e) T.-A. Mitsudo, N. Suzuki, T.-A. Kobayashi
and T. Kondo, J. Mol. Cat. A: Chem., 1999, 137, 253–262; f) M. A.
Moreno, M. Haukka, S. Jääskeläinen, S. Vuoti, J. Pursiainen and T. A.
Pakkanen, J. Organomet.
Chem., 2005, 690, 3803–3814; g) M. Moreno,
M. Haukka, A. Turunen and T. Pakkanen, J. Mol. Cat. A: Chem., 2005,
240, 7–15; h) L. Wu, I. Fleischer, R. Jackstell, I. Profir, R. Franke and M.
Beller, J. Am. Chem. Soc., 2013, 135, 14306–14312; i) I. Fleischer, K.
M. Dyballa, R. Jennerjahn, R. Jackstell, R. Franke, A. Spannenberg
and M. Beller, Angew. Chem. Int. Ed., 2013, 52, 2949–2953;
K. Takahashi, M. Yamashita and K. Nozaki, J. Am. Chem. Soc., 2012,
134, 18746–18757.
[8]
[9]
K. Takahashi, M. Yamashita, T. Ichihara, K. Nakano and K. Nozaki,
Angew. Chem. Int. Ed., 2010, 49, 4488–4490.
[10] D. G. Hanna, S. Shylesh, P. A. Parada and A. T. Bell, J. Catal., 2014,
311, 52–58.
[11] Y. Yuki, K. Takahashi, Y. Tanaka and K. Nozaki, J. Am. Chem. Soc.,
2013, 135, 17393–17400.
[12] a) M. van der Steen, C. V. Stevens, ChemSusChem 2009, 2, 692–713.
b) H. Mutlu, M. A. R. Meier, Eur. J. Lipid Sci. Technol. 2010, 112, 10–
30.
Acknowledgements
[13] a) O. Türünç, M. A. R. Meier, Eur. J. Lipid Sci. Technol. 2013, 115, 41–
54; b) J. Ternel, J.-L. Couturier, J.-L. Dubois, J.-F. Carpentier, Adv.
Synth. Catal. 2013, 355, 3191–3204; c) C. Bruneau, P. H. Dixneuf, C.
Fischmeister, X. Miao, J.-L. Dubois, J.-L. Couturier, ChemSusChem
2012, 5, 1410–1414; d) M. Winkler, M. A. R. Meier, Green Chem. 2014,
16, 3335–3340. e) A. Behr, S. Toepell, S. Harmuth, RSC Adv. 2014, 4,
16320–16326 ; f) C. Jiménez-Rodriguez, A. A. Núnez-Magro, T.
Seidensticker, G. R. Eastham, M. R. L. Furst, D. J. Cole-Hamilton,
Catal. Sci. Technol. 2014, 4, 2332–2339 ; g) M. R. L. Furst, T.
Seidensticker, D. J. Cole-Hamilton, Green Chem. 2013, 15, 1218–1225.
h) T. Gaide, A. Behr, A. Arns, F. Benski, A. J. Vorholt, Chem. Eng.
Process. Process Intensif. 2016, 99, 197-204. i) T. Witt, F. Stempfle, P.
Roesle, M. Häußler, S. Mecking, ACS Catal. 2015, 5, 4519–4529.
[14] D. Quinzler and S. Mecking, Angew. Chem. Int. Ed., 2010, 49, 4306–
4308.
We gratefully acknowledge the financial support of the German
Science Foundation (Project SFB/TRR 63: ”InPROMPT
–
Integrated Chemical Processes in Multi-Phase Fluid Systems”)
for this work (Subproject A1). We would also like to express our
gratitude to Umicore AG & Co. KG for supplying the catalyst
precursors.
Keywords: Hydroformylation; Crystallization; Renewable
Feedstocks; Tandem Catalysis
[1]
a) A. Börner and R. Franke, Hydroformylation: fundamentals processes
and applications in organic synthesis, Wiley-VCH, Weinheim, 2016. b)
G. Frey and G. Dämbkes, 75 Jahre Oxo-Synthese. = 75 years of oxo
synthesis, Klartext, Essen, 2013.
[15] T. Seidensticker, H. Busch, C. Diederichs, J. J. von Dincklage, A. J.
Vorholt, ChemCatChem, 2016, 8, 2890-2893.
[2]
[3]
[4]
G. M. Torres, R. Frauenlob, R. Franke and A. Börner, Catal. Sci.
Technol., 2015, 5, 34–54.
[16] [a] A. Behr, D. Obst, A. Westfechtel, Eur. J. Lipid Sci. Technol., 2005,
107, 213–219. [b] J. Ternel, J.-L. Couturier, J.-L. Dubois, J.-F.
Carpentier, Adv. Synth. Catal., 2013, 355, 3191–3204. [c] T. Gaide, J.
Bianga, K. E. Schlipkoeter, A. Behr, A. J. Vorholt, ACS Catalysis, 2017,
accepted, DOI: 10.1021/acscatal.7b00249.
A. Behr, A. J. Vorholt, K. A. Ostrowski, T. Seidensticker, Green Chem.
2014, 16, 982–1006.
a) L. H. Slaugh and R. D. Mullineaux, J. Org. Chem., 1968, 13, 469–
477; b) M. Beller and J. G. Krauter, J. Mol. Cat. A, 1999, 143, 31–39; c)
This article is protected by copyright. All rights reserved.

10.1002/cctc.201700965
ChemCatChem
COMMUNICATION
[17] D. Prat, A. Wells, J. Hayler, H. Sneddon, C. R. McElroy, S. Abou-
Shehada and P. J. Dunn, Green Chem. 2016, 18, 288–296.
[18] T. Gaide, J. M. Dreimann, A. Behr and A. J. Vorholt, Angew. Chem. Int.
Ed., 2016, 55, 2924–2928.
[19] J. M. Dreimann, M. Skiborowski, A. Behr and A. J. Vorholt,
ChemCatChem, 2016, 8, 3330–3333.
This article is protected by copyright. All rights reserved.

10.1002/cctc.201700965
ChemCatChem
COMMUNICATION
Entry for the Table of Contents (Please choose one layout)
Layout 2:
COMMUNICATION
M. R. L. Furst, V. Korkmaz, T. Gaide, T.
Seidensticker, A.Behr and A. J. Vorholt*
Page No. – Page No.
Tandem Reductive Hydroformylation
of Castor Oil Derived Substrates and
Catalyst Recycling by Selective
Product Crystallisation
Linear bifunctional polymer precursors were conveniently synthesized from castor
oil derived renewalbe substrates by applying an orthogonal tandem system
conisting of two in situ formed catalytic species. Selective product crystallization
was developed ensuring both, the recovery of the active tandem system and
providing a high purity monomer.
This article is protected by copyright. All rights reserved.