Dual Rh?Ru Catalysts for Reductive Hydroformylation of Olefins to Alcohols

Article abstract of DOI:10.1002/cssc.201800488

An active and selective dual catalytic system to promote domino hydroformylation–reduction reactions is described. Apart from terminal, di- and trisubstituted olefins, for the first time the less active internal C?C double bond of tetrasubstituted alkenes can also be utilized. As an example, 2,3-dimethylbut-2-ene is converted into the corresponding n-alcohol with high yield (90 %) as well as regio- and chemoselectivity (>97 %). Key for this development is the use of a combination of Rh complexes with bulky monophosphite ligands and the Ru-based Shvo's complex. A variety of aromatic and aliphatic alkenes can be directly used to obtain mainly linear alcohols.

Full text of DOI:10.1002/cssc.201800488

Accepted Article
Title: Dual Rh-Ru catalysts for reductive hydroformylations of olefins to
alcohols
Authors: Fabio Rodrigues, Peter Kucmierczyk, Marta Pineiro, Ralf
Jackstell, Robert Franke, Mariette Pereira, and Matthias
Beller
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10.1002/cssc.201800488
ChemSusChem
COMMUNICATION
Dual Rh-Ru catalysts for reductive hydroformylations of olefins to
alcohols
Fábio M. S. Rodrigues[a], Peter K. Kucmierczyk[b,c], Marta Pineiro[a], Ralf Jackstell[b], Robert Franke[c,d]
Mariette M. Pereira*[a] and Matthias Beller*[b]
,
Abstract: An active and selective dual catalytic systems to promote
domino hydroformylation/reduction reactions are described. Apart
from terminal, di- and tri-substituted olefins for the first time also less
active internal C-C double bond of tetra-substituted alkenes can be
utilized. As an example, 2,3-dimethylbut-2-ene is converted to the
corresponding n-alcohol with high yield (90%) as well as regio- and
chemoselectivity (>97%). Key for this development is the use of a
combination of Rh complexes with bulky monophosphites and the
Ru-based Shvo‘s-complex. A variety of aromatic and aliphatic
alkenes can be directly used to obtain mainly linear alcohols.
The functionalization of highly substituted olefins such as 2,3-
dimethylbut-2-ene and the industrial feedstock dibutene via
carbonylation reactions[1] is currently a topic of high industrial
interest. Especially the efficient conversion of these substrates
into high value linear alcohols is still a great challenge. Oxo
alcohols are an important class of industrial products, which are
currently produced by tandem hydroformylation/hydrogenation of
olefins catalysed by several metal complexes[2] including Ru[3],
Rh[4] and Pd[5] The most prominent representative is the Shell
Table 1. Hydroformylation/reduction of 2,3-dimethylbut-2-ene 1 using dual
catalyst systems.[a]
Yield (%)[b]
Conv.
Entry
Ligand
Catalyst
(%)[b]
2
3
4
,
.
Oil Co. process, which uses a cobalt-phosphine catalyst system
to produce linear higher alcohols from regular internal higher
olefins.[6] Nowadays, n-butanol, 2-ethylhexanol and isobutanol
constitute main examples with an estimated market >12 Mio
tons/a and growing ca. 4.4% until 2020.[7] In order to improve the
synthesis of oxo alcohols, there exist a continuing interest in
academia and industry to develop improved catalytic systems.[8]
With respect to the principles of green chemistry, it is especially
desirable to improve the step economy for these products.[9] In
this respect, combination of hydroformylation and reduction –
1
2
3
4
5
6
-
Xantphos
L1
Rh(CO)2acac
Rh(CO)2acac
Rh(CO)2acac
Rh(CO)2acac
Rh(CO)2acac
Rh(CO)2acac
61
60
84
62
82
80
3
2
4
5
4
5
49
48
77
56
75
70
9
10
3
L2
1
L3
3
L4
5
Rh(CO)2acac +
Shvo’s catalyst
7
L1
88
46
40
2
Rh(CO)2acac +
Shvo’s catalyst
8
9
-
-
65
29
42
11
14
6
9
so-called hydrohydroxymethylation
–
would allow for
a
Shvo’s catalyst
12
straightforward and atom efficient access to alcohols directly
from easily available olefins and syngas. Due to the price of
feedstocks, the selective conversion of mixtures of terminal and
internal alkenes like for example refinery mixtures would be
[a] Reaction conditions: 2,3-dimethylbut-2-ene
1
(10.0 mmol),
[Rh(CO)2acac] (7.7 μmol), L (15.4 μmol), Shvo’s-complex (3.8 μmol),
solvent: 30 mL of toluene, CO (12 bar) and H2 (25 bar) at 120 °C for 20 h.
[b] Determined by GC, using isooctane as external standard.
[a]
[b]
[c]
[d]
F. M. S. Rodrigues, Prof. Dr. M. Pineiro, Prof. Dr. M. M. Pereira
CQC, Departamento de Química
Universidade de Coimbra
Rua Larga, 3004-535 Coimbra (Portugal)
P. K. Kucmierczyk, Dr. R. Jackstell, Prof. Dr. M. Beller,
Leibniz-Institut für Katalyse e.V.an der Universität Rostock
Albert-Einstein-Str. 29a, 18059 Rostock (Germany)
E-mail: matthias.beller@catalysis.de
P. K. Kucmierczyk, Prof. Dr. R. Franke
Lehrstuhl für Theoretische Chemie
Ruhruniversität Bochum
Universitätsstraße 150, 44801 Bochum (Germany)
Prof. Dr. R. Franke
Evonik Industries AG
Paul-Baumann-Straße. 1, 45772 Marl, (Germany)
even more desirable.[10] In principle, combining the isomerization
of internal to terminal olefins, followed by the n-selective
hydroformylation, and subsequent hydrogenation of the obtained
aldehyde allows for an ideal synthesis of n-alcohols. However,
so far only few catalysts are known that promote the
transformation of olefins directly to alcohols.[11] An important
achievement was reported by Nozaki and co-workers in 2010,
who described a tandem hydroformylation/hydrogenation of 1-
decene to undecanol in over 90% yield using a bimetallic
catalyst consisting of Rh-xantphos and Shvo´s-complex.[12] This
complex is a well-known example of an hydrogenation catalyst
that operates by an outer sphere mechanism.[13] Later in 2012,
this group reported the scope and limitation of their dual catalyst
Supporting information for this article is given via a link at the end of
the document
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10.1002/cssc.201800488
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COMMUNICATION
linear alcohols in the presence of ruthenium complexes with P-N
ligands.[11a,11b,11d] Despite the lower price of ruthenium compared
to rhodium, also this catalyst was limited to terminal olefins.
Taking into account the high activity and selectivity of
Rh/phosphite catalysts in the hydroformylation of aliphatic and
aromatic olefins,[15] herein we describe a new and practical
Rh/Ru catalyst system for the selective functionalization of all
kinds of olefins. Applying a combination of Rh/tris-binaphthyl-
based helical monophosphites and Shvo’s-complex,[16] promotes
even the transformation of highly substituted olefins such as 2,3-
dimethylbutene and the industrial feedstock dibutene.
Table 2. Rhodium/phosphite/ruthenium-catalyzed hydroformylation/reduction
of 2,3-dimethylbut-2-ene: Optimization of reaction conditions.[a]
Yield (%)[b]
pH2
pCO
T
VSol.
(mL)[c]
Conv.
(%)[b]
Entry
(bar)
(bar)
(°C)
2
3
4
To improve the known catalysts for a general synthesis of
alcohols from olefins, the reaction of 2,3-dimethylbut-2-ene 1 to
give 3,4-dimethylpentan-1-ol 2 was chosen as a model system.
In general, test reactions were performed at 120 °C for 20 hours
in the presence of 0.077 mol% of [Rh(CO)2acac] and 0.154
mol% of ligands under 12 bar CO and 25 bar H2. In order to
speed up the hydrogenation step, 0.038 mol% of the Shvo’s-
complex was added in some experiments. Initially, the effect of
different ligands on activity and selectivity was evaluated. For
this purpose reactions were carried out in the presence of
[Rh(CO)2acac] and different tris-binaphthyl-based helical
monophosphites L1-L3 in comparison to Xantphos (Table 1).
1
2
3
4
5
6
7
8
10
20
30
50
30
30
30
30
10
10
10
10
10
10
10
10
120
120
120
120
80
30
30
30
30
30
30
20
5
71
75
81
97
10
24
93
90
28
44
77
91
0
38
31
0
4
0
4
6
1
0
3
2
0
9
100
120
120
0
24
0
90
88
0
[a] Reaction conditions: 2,3-dimethylbut-2-ene 1 (10.0 mmol), [Rh(CO)2acac]
(7.7 μmol), L1 (15.4 μmol), Shvo’s-complex (3.8 μmol), solvent: toluene, 20 h.
[b] Determined by GC, using isooctane as external standard. [c] For VSol = 5
mL a 40 mL autoclave was used instead of a 100 mL autoclave.
The latter ligand was previously applied by Nozaki and co-
12, 14]
workers,[11c,
while the former ligands were previously
applied by some of us for highly regioselective rhodium-
catalyzed hydroformylation reactions of internal olefins.[17]
system for the production of linear α,ω-diols.[14] More recently,
As shown in Table 1 (entry 1), the hydroformylation in the
absence of any phosphorous ligand gave 61% of conversion
and 49% yield for aldehyde 3 as well as 3% of the desired
alcohol 2. Similarly, in the presence of Xantphos as ligand only
tiny amounts (2%) of the desired alcohol 2 were obtained (60%
conversion, 48% aldehyde 3, 10% hydrogenated product 4;
Table 1, entry 2). The use of bulky phosphite π–acceptor ligands
they
developed
a
modified
catalyst
for
system
one-pot
(Rh/bisphosphite/Shvo´s-complex)
isomerization/hydroformylation/hydrogenation of internal alkenes
to linear alcohols. Unfortunately, only moderate reaction rates
(up to 36 h reaction time) were achieved and tri- and tetra-
substituted olefins were not applied.[11c] In 2013, some of us
described an alternative process to promote the domino
hydroformylation/reduction of terminal and internal olefins to
is known to increase significantly the activity and selectivity for
[18]
the formation of aldehydes.
Hence, to improve the results of
the Rh/Xantphos catalyst system, we employed phosphites as
ligands.[17] Although tris-binaphthyl monophosphites L1-L3
achieved improved conversion of 84%, 62% and 82%,
respectively, the formation of the alcohol was still negligible
(<5%; Table 1, entries 3-5). Moreover, for comparison with our
system we also performed an experiment, according the
conditions to entry 3-5 in Table 1, using tris(2,4-di-tert-
butylphenyl) phosphite (L4) as ligand instead.
100
90
80
70
2,3-dimethylbut-2-ene
2,3-dimethylbutane
3,4-dimethylpentanal
3,4-dimethylpentanol
60
50
40
30
20
10
0
0
2
4
6
8
10 12 14 16 18 20 22 24
Raction time (h)
Figure 1. Reaction progress of hydroformylation/reduction of 2,3-dimethylbut-
2-ene 1: Substrate and product yield vs. time. Reaction conditions: 1 (40.0
mmol), [Rh(CO)2acac] (30.8 μmol), L1 (61.6 μmol), Shvo’s-complex (15.2
μmol), toluene (20 mL), with 40 bar initial pressure (pCO = 10 bar, pH2 = 30 bar),
reactor is connected to a constant feed of CO:H2 (1:2) to keep pressure and
ratio of syngas mixture constant during the reaction time, T = 120 °C. Yield
determined by GC analysis, using isooctane as external standard.
Scheme 1. Proposed route for the conversion of olefin to desired alcohol.
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Similar activity was obtained (80% conversion). Nevertheless
selectivity for aldehyde 3 (70% yield) was lower while the yield
of hydrogenated product 4 increased to 5% (Table 1, entries
6). To improve the final hydrogenation step of the aldehyde,
0.038 mol% of the Shvo’s-complex was added to the Rh/L1
system (Table 1, entry 7). To our delight, the application of
this dual catalyst improved considerably the selectivity and did
not reduce the overall activity (Table 1, entries 3 and 7).
Hence, alcohol 2 was obtained as the major product in 46%
yield. However, performing the reaction without L1 (Table 1,
entry 8) or without the Rh/L1 combination (Table 1, entry 9)
the conversion was significantly lower (65% and 29%). In the
presence of only the Shvo´s-complex equal amounts of
alcohol 2 and undesired alkane 4 were obtained. As expected,
experiments performed in the absence of any metal in the
presence or absence of ligand did not give any conversion.
Next, we investigated the reaction conditions (CO and
H2 total and partial pressure, temperature and reactant
concentration) in more detail to improve this Rh-L1/Ru-
Shvo’s-complex further on (Table 2). Reducing the hydrogen
content (1:1 CO/H2 syngas mixture under 20 bar pressure) led
to a conversion of 71% with aldehyde 3 being obtained as the
major product (38%), and the desired alcohol 2 being formed
in only 28% (Table 2, entry 1). Increasing the H2 partial
pressure (20, 30 and 50 bar) while keeping CO initial pressure
at 10 bar, improved conversions to 75, 81 and 97%,
respectively and led to better yields for the desired alcohol 2
(44, 77 and 91%, respectively) (Table 2, entries 2-4). In order
to identify additional positive effects, all subsequent studies
were performed using a syngas pressure of 40 bar (H2/CO
3:1).
Table 3. Ruthenium/phosphite/rhodium-catalyzed hydroformylation/reduction of
2,3-dimethylbut-2-ene: Optimization of reaction conditions.[a]
Yield (%)
Yield
Entry
Substrate
Major product
Major Product
c (%)
[n/i]
1
2
3
94 [99/1]
24 [25/75]
88
5
2
10
4
54
43
5
6
37 [71/29]
45 [87/13]
48
48
7
95 [99/1]
5
Despite the temperature-sensitive activity of Shvo’s-
complex, we searched for milder reaction conditions of the
bimetallic system.[11c, 14] As expected, for lower temperatures
(80 °C and 100 °C) conversions were significantly lower (10%
and 24%), with almost exclusive formation of aldehyde 3
(Table 2, entries 3, 5-6). On the other hand, we were able to
reduce the amount of solvent from 30 mL to 20 mL and 5 mL
without decrease in activity or selectivity of desired alcohol 2
(Table 2, entries 3 and 7-8). This latter result demonstrates
the potential viability of this catalytic system for industrial
transposition. In addition we also evaluated the viability of the
use of racemic L1 counterpart as ligand in the previous best
conditions and slightly lower activity was obtained (80%
conversion) with the same alcohol selectivity (77% yield).
To understand the mechanism of this domino-reaction
and to identify intermediates, the reaction progress was
measured and aliquots were taken, at regular intervals, from
the mixture within 24 h. The yield of corresponding products
and remaining substrate is plotted in Figure 1.
8
9
68 [70/30]
37 [29/71]
3
16
10
11
29 [55/45]
43 [33/67]
43
36
12
13
45 [90/10]
45 [35/65]
50
30
As shown in Figure 1, the isomerized terminal olefin 5 (see
also Scheme 1) is not detected. Hence, we conclude that the
rate constant k2 (hydroformylation of 5) is significantly higher
than k1 (isomerization of 1). Along the first 3 h the built-up of
the aldehyde occurs. After this period the aldehyde yield start
to decrease suggesting the rate of the hydrogenation step is
higher than the hydroformylation.
[a] Reaction conditions: alkene (4.0 mmol), [Rh(CO)2acac] (3.1 μmol), L1 (6.2
μmol), Shvo’s-complex (1.5 μmol),CO (10 bar), H2 (30 bar), solvent: toluene (2
mL), 20 h at 120 °C. Conversions were in all cases 98%. Determined by GC-MS.
[b] Mixture of C8-alkene which mainly consist of methyl-heptene (75%), 3,4-
dimethyl-hexene (15%), octane (9%). [c] Corresponding C9-n-alcohols of
dibutene. [d] Alkene (3.0 mmol).
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double bond increased to 43%. Interestingly, imide and ester
functionalities were well tolerated (Table 3, entries 11 and 12)
and the corresponding alcohols were isolated in reasonable
yields (63% and 50%, respectively). Finally, the reactivity of the
unsaturated aldehyde 18 was tested. Gratifyingly, industrially
relevant long chain alcohols and diols were formed exclusively
(Table 3, entry 13).
Then, the substrate scope was extended to naturally
occurring di- and tri-substituted olefins 19-21. These
transformations are of general interest in the context of
valorisation of renewable feedstocks. As shown in Scheme 2
conversions were in all cases >99%. For methyl oleate 19 the
hydroformylation/reduction of the internal double bond led to
major formation of branched oxo alcohols 19b, which are
compounds with great relevance for industrial applications.[19]
This observation is in agreement with previous results obtained
Scheme
2.
Ruthenium/phosphite/rhodium-catalyzed
hydroformylation/reduction of industrial/biological relevant substrates.[a]
using
a
Rh/bulky
phosphite
system
for
related
hydroformylations.[20] Moreover, the tri-substituted terpene
citronellol 20 was used as substrate. Here, chemoselective
formation of alcohols was observed in 80% to give the linear oxo
diol 20a, resulting from the isomerization/hydroformylation/
reduction, as the major product (51%, Scheme 2).
As an example of a bio-active steroid derivative, the reaction
was extended to stigmasterol 21 leading to alcohols with 61%
chemoselectivity. Here, the linear alcohol 21a was identified by
NMR spectroscopy as the major product in 43% yield.
[a] Reaction conditions: alkene (10.0 mmol), [Rh(CO)2acac] (7.7 μmol), L1
(15.4 μmol), Shvo’s-complex (3.8 μmol), CO (10 bar), H2 (30 bar), solvent:
toluene (5 mL), 20 h at 120 °C. Conversions were in all cases 99%.
Determined by GC-MS. [b] Reaction conditions: steroid (0.48 mmol),
[Rh(CO)2acac] (9.8 μmol), L1 (19.6 μmol), Shvo’s-complex (4.9 μmol), p(CO)
= 10 bar, p(H2) = 30 bar, solvent: toluene (3 mL), 48 h at 120 °C. Conversion
determined by NMR analysis of the reaction crude. Conversions were, in all
cases, 99%.
Conclusion
In summary, we have developed an active and selective dual
catalytic system to promote tandem hydroformylation/reduction
reactions. Compared with previously known catalysts, our
system promotes the direct hydroformylation/reduction of less
active internal C-C double bonds. Hence, the conversion of
highly substituted alkenes to mainly linear alcohols is possible
for the first time. Key for this development is the use of a
combination of Rh complexes with bulky monophosphites and
the well-known Ru-based Shvo’s-complex. The results
presented here pave the way for more efficient preparation of
value-added oxo alcohols from inexpensive industrial feedstocks
or renewables.[21]
Finally, the applicability of this domino hydroformylation-
hydrogenation methodology was evaluated for a series of
aromatic and aliphatic olefins (Table 3). For the majority of
substrates, good yields of the corresponding alcohols were
obtained at 120 °C using 40 bar of synthesis gas (H2/CO 3:1).
Internal and terminal mono- and di-substituted aromatic olefins
(Table 3, entries 1-4) as well as aliphatic di- and tri- substituted
pure alkenes and mixtures of them (Table 3, entries 6-8) were
successfully transformed to desired alcohols with the
Rh/L1/Shvo’s-complex. Except for substrates 9-11, which gave
significant amounts of the respective alkanes, very good alcohol
yields were obtained. Interestingly, hydroformylation/reduction of
1,1-disubstituted as well as tri-substituted olefins leads in high
regioselectivity to the linear oxo alcohol (Table 3, entries 1, 6-8).
However, in the case of trans-1,2-disubstituted (E)-prop-1-en-1-
ylbenzene 7 the branched alcohols 7b (73% yield) were mainly
obtained due to the thermodynamic stabilization of the
intermediate rhodium benzyl complex (Table 3, entry 2).
Noteworthy, the excellent chemoselectivity of 97% for alcohols is
the result of the high activity of our bimetallic catalyst system.
Next, under the same reaction conditions different functionalized
olefins were investigated (Table 3, entries 9-13).
Experimental Section
General method for the hydroformylation/reduction of alkenes: A 100 mL
steel autoclave was charged with [Rh(CO)2acac] (1.98 mg, 7.7 μmol),
tris[(R)-2'-(benzyloxy)-1,1'-binaphthyl-2-yl] phosphite ligand L1 (17.8 mg
15.4 μmol) and Shvo’s-complex (4.1 mg, 3.8 μmol). The autoclave was
closed and the air was removed using a vacuum pump. Then, the
desired amount of dry toluene and the alkene (10 mmol) were added
through cannula. After flushing the autoclave with H2/CO, it was
pressurized with the desired amount of H2/CO gas and heated to 120 °C
with magnetic stirring. After 20 h, the autoclave was cooled with ice water
and the pressure was released. The crude reaction mixture was diluted
with toluene and analyzed by gas chromatography, using isooctane as
external standard.
Similar to substrate 7, 1-methoxy-4-propenylbenzene 14 gave
the branched alcohols 14b (n/i 29/71) as major products. In
addition, alcohol 15a is obtained by isomerization of trans-3-
phenyl-2-propen-1-ol 15 with a regioselectivity of 55% (Table 3,
entry 10). Besides, in this case direct hydrogenation of the
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10.1002/cssc.201800488
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COMMUNICATION
[15]
a) R. M. B. Carrilho, A. C. B. Neves, M. A. O. Lourenço, A. R.
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Non-commercially available products presented in the Table 3 and
Scheme 2 were isolated by chromatography and the characterization
data is presented in the SI.
[16]
[17]
Acknowledgements
The authors thank Fundação para a Ciência e Tecnologia (FCT)
for the financial support to Coimbra Chemistry Centre (PEst-
OE/QUI/UI0313/2014). To the projects POCI-01-0145-FEDER-
016387, H2020 AAC/02/SAICT/2017/027996 and to UC-NMR
facility which is supported in part by FEDER through the
COMPETE programme and by National Funds through FCT
grants RECI/QEQ-QFI/0168/2012, CENTRO-07-CT62-FEDER-
002012. F.M.S.R. also thank FCT for the grant
(PD/BD/114340/2016). This research was supported by Evonik
Performance Materials GmbH and the State of Mecklenburg-
Vorpommern as well as Leibniz Association (Leibniz
Competition, SAW-2016-LIKAT-1). We thank the analytical
teams at Coimbra and Rostock for their kind support.
[18]
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L. Damas, G. N. Costa, J. C. Ruas, R. M. B. Carrilho, A. R. Abreu,
G. Aquino, M. J.F. Calvete, M. Pineiro, M. M. Pereira, Curr.
Microwave Chem. 2015, 2, 53-60.
M. Beller, G. Centi, L. Sun, ChemSusChem 2017, 10, 6-13.
Keywords: hydroformylation • hydrogenation• linear alcohol•
rhodium• ruthenium
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This article is protected by copyright. All rights reserved.

10.1002/cssc.201800488
ChemSusChem
COMMUNICATION
COMMUNICATION
Paving the way for more efficient
preparation of value-added oxo
alcohols: An active and selective dual
catalytic system to promote one-pot
hydroformylation/reduction reactions
is described. The combination of Rh
complexes with bulky monophosphites
and the well-known Ru-based Shvo’s-
complex is the key for the high yield of
oxo-alcohols.
Fábio M. S. Rodrigues, Peter K.
Kucmierczyk, Marta Pineiro, Ralf
Jackstell, Robert Franke, Mariette M.
Pereira and Matthias Beller*
Page No. – Page No.
Dual Rh-Ru catalysts for reductive
hydroformylations of olefins to
alcohols
This article is protected by copyright. All rights reserved.