Intermolecular coupling of alkynes with acrylates by recyclable oxide-supported ruthenium catalysts: Formation of distorted ruthenium(IV)-oxo species on ceria as a key precursor of active species

Article abstract of DOI:10.1002/adsc.201100415

A solid ceria-supported ruthenium catalyst (Ru/CeO₂) as well as a zirconia-supported ruthenium catalyst (Ru/ZrO₂) showed high activities toward the intermolecular coupling of alkynes with acrylates to give the corresponding 1,3-dienes in high yields. The reaction proceeded in the presence of sodium formate and both internal or terminal alkynes and norbornene could be applied for the catalytic systems. The solid ruthenium catalyst could be recycled for several times without significant loss of activity. The FT-IR and X-ray absorption fine structure (XAFS) studies of ceria-supported ruthenium catalysts showed that a distorted ruthenium(IV)-oxo species on ceria was transformed during the initial stage of the reaction into a low-valent ruthenium species that was effective for the coupling reactions. Copyright

Full text of DOI:10.1002/adsc.201100415

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DOI: 10.1002/adsc.201100415
Intermolecular Coupling of Alkynes with Acrylates by Recyclable
Oxide-Supported Ruthenium Catalysts: Formation of Distorted
Ruthenium(IV)-oxo Species on Ceria as a Key Precursor of
Active Species
Hiroki Miura,a Shun Shimura,a Saburo Hosokawa,a Seiji Yamazoe,b Kenji Wada,a,*
and Masashi Inouea,*
a
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Katsura,
Nishikyo-ku, Kyoto 615-8510, Japan
Fax : (+81)-75-383-2479; phone: (+81)-75-383-2482; e-mail: wadaken@scl.kyoto-u.ac.jp or inoue@scl.kyoto-u.ac.jp
Department of Materials Chemistry, Graduate School of Science and Technology, Ryukoku University, Seta, Otsu
b
520-2194, Japan
Received: May 21, 2011; Published online: October 10, 2011
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.201100415.
Abstract: A solid ceria-supported ruthenium catalyst FT-IR and X-ray absorption fine structure (XAFS)
(Ru/CeO2) as well as a zirconia-supported ruthenium studies of ceria-supported ruthenium catalysts
catalyst (Ru/ZrO2) showed high activities toward the showed that a distorted ruthenium(IV)-oxo species
intermolecular coupling of alkynes with acrylates to on ceria was transformed during the initial stage of
give the corresponding 1,3-dienes in high yields. The the reaction into a low-valent ruthenium species that
reaction proceeded in the presence of sodium for- was effective for the coupling reactions.
mate and both internal or terminal alkynes and nor-
À
bornene could be applied for the catalytic systems. Keywords: C C coupling; ceria; ruthenium; support-
The solid ruthenium catalyst could be recycled for ed catalysts; XAFS; X-ray absorption fine structure
several times without significant loss of activity. The (XAFS)
Introduction
ineffective for these reactions, which demonstrates
the specific effects of the combination of Ru species
Highly efficient organic transformations with solid and CeO2 or ZrO2.
catalysts,[1] in particular inorganic oxide-supported
On the other hand, substituted 1,3-dienes are im-
catalysts, contribute to the realization of green sus- portant organic intermediates in modern industrial
tainable chemistry,[2] since they can provide benefits chemistry and materials science.[9] Various methods
such as simple and low-cost preparation, high thermal for their preparation through the use of organometal-
and chemical stabilities, and facile recovery and recy- lic reagents have been proposed.[10] Above all, the in-
cling of the catalysts.[3] In general, the states of sup- termolecular coupling of alkynes with alkenes is one
ported metal species are critically affected by the sup- of the most atom-efficient strategies and has been
ports, and a particular support may completely achieved with a series of transition metal complex cat-
change the nature of the metal species, which could alysts, including Ru,[11] Rh,[12] Pd,[13] Co[14] and Ni.[15]
show unexpected features in catalytic reactions.[4]
However, these homogeneous complex catalysts are
Recently, we reported various efficient organic difficult to prepare, highly sensitive toward air and
À
transformations, such as the arylation of aromatic C
moisture, and they often require the use of toxic
H bonds, in the presence of Ru/CeO2 and Ru/ZrO2 phosphines as ligands for efficient catalysis. To the
catalysts.[5–8] These simple catalysts could be recycled best of our knowledge, there has been no example of
several times without a significant loss of ruthenium the synthesis of substituted 1,3-dienes via the intermo-
species from the oxide support. Ruthenium catalysts lecular coupling of alkynes with alkenes by simple,
supported on SiO2, Al2O3, TiO2 and MgO were totally stable and recyclable solid catalysts. Herein, we de-
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scribe the first examples of the intermolecular cou- (125 mg, 0.025 mmol as Ru) together with a catalytic
pling of alkynes with acrylates by oxide-supported amount of sodium formate in N,N-dimethylacetamide
catalysts, Ru/CeO2 and Ru/ZrO2, in the presence of (DMA) at 1108C for 3 h gave 1,3-diene 3a in a yield
sodium formate. Furthermore, the coupling of two dif- of 98% with high Z selectivity at the g,d-position
ferent alkenes was also realized through the use of (Table 1, entry 1). No reaction occurred in the ab-
these simple catalysts. The solid catalysts could be re- sence of sodium formate, even at a higher tempera-
cycled several times without a significant loss of activ- ture (entries 2 and 3). The use of sodium acetate in-
ity. A detailed characterization of the supported Ru stead of sodium formate did not afford 3a at all
catalysts suggests that the distorted Ru(IV)-oxo spe- (entry 4). The treatment of Ru complexes by formate
[16,17a]
À
cies is present in the ceria support which then was has been reported to produce Ru H species,
transformed into low-valent Ru species at the initial which were thought to play a key role in the present
stage of the reaction, leading to efficient catalytic re- coupling reaction.[17] The addition of sodium borohy-
actions.
dride, 2-propanol or isobutyryl chloride as hydride
sources to the reaction mixture was ineffective, and
the reaction under an H2 atmosphere resulted in a
low yield of 3a (entries 5–8). The addition of PPh3
completely suppressed the reaction (entry 9), al-
Results and Discussion
Supported Ru catalysts were prepared as follows: an though ruthenium phosphine complexes have been re-
oxide support was added to a THF solution of ported to be effective precursors for homogeneous
Ru
the resulting powder was calcined in air to afford the
ACHTUNGTRENNUNG
(acac)3 at room temperature. After impregnation, catalysts.[11c,g]
Among other supported Ru catalysts examined,
supported Ru catalyst, designated as Ru/support- Ru/ZrO2 showed high activity (entry 10). In contrast,
XXcal (where XX indicates the calcination tempera- no reaction took place with Ru catalysts supported on
ture in Celsius). The loading of ruthenium was SiO2, Al2O3, TiO2 or MgO (entries 11–14). Note that
2.0 wt%.
air- and moisture-stable Ru complexes, Ru
ACHTUNGTRENNUNG(acac)3,
The reaction of diphenylacetylene (1a) with methyl RuCl3·nH2O and [RuCl2ACTHUNGTR(NENNUG p-cymene)]2, were not very
acrylate (2a) in the presence of Ru/CeO2-400cal effective under the present conditions (entries 15–17).
Table 1. Effects of additives and supports.
Entry
Ru catalyst
Additive [mmol]
Yield [%][a,b]
1
Ru/CeO2-400cal
Ru/CeO2-400cal
Ru/CeO2-400cal
Ru/CeO2-400cal
Ru/CeO2-400cal
Ru/CeO2-400cal
Ru/CeO2-400cal
Ru/CeO2-400cal
Ru/CeO2-400cal
Ru/ZrO2-400cal
Ru/SiO2-400cal
Ru/Al2O3-400cal
Ru/TiO2-400cal
Ru/MgO-400cal
HCO2Na (0.15)
–
–
98 (93:7)
0
0
0
8
0
0
11
trace
93 (95:5)
0
trace
0
trace
trace
21
2
3[c]
4
CH3CO2Na (0.15)
NaBH4 (0.15)
2-PrOH (0.30)
isobutyryl chloride (0.15)
H2 (1 atm)
HCO2Na (0.15); PPh3 (0.050)
HCO2Na (0.15)
HCO2Na (0.15)
HCO2Na (0.15)
HCO2Na (0.15)
HCO2Na (0.15)
HCO2Na (0.15)
HCO2Na (0.15)
HCO2Na (0.15)
5
6
7
8[d]
9
10
11
12
13
14
15
16
17
Ru
RuCl3·nH2O
[RuCl2A(p-cymene)]2
ACHTUNGERTN(NUNG acac)3
A
U
15
[a]
Determined by GLC.
g,d-Z/E-Selectivities in parentheses.
Reaction at 1708C.
[b]
[c]
[d]
Reaction under H2 (1 atm) atmosphere.
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Intermolecular Coupling of Alkynes with Acrylates by Recyclable Oxide-Supported Ruthenium Catalysts
Scheme 1. Proposed structure of ruthenium(IV) oxo species
on the CeO2 and ZrO2 before the catalytic run.
TiO2 or MgO as previously reported.[6] On the other
hand, the formation of Ru-oxo species on ZrO2 has
been proposed previously.[19,20] These results suggest
that the combination of Ru with CeO2 or ZrO2 cre-
ates the highly dispersed Ru(IV)-oxo species with a
distorted coordination environment as shown in
Scheme 1.[5,18,19]
Figure 1. Ru K-edge (a) FT of EXAFS and (b) XANES
spectra of supported Ru catalysts calcined at 4008C.
The calcination temperature of the catalysts greatly
affected the fine structure of Ru species on CeO2
Although we have previously reported Ru/CeO2- (Figure 2a). The XANES spectrum of Ru/CeO2
and Ru/ZrO2-catalyzed organic synthetic reactions,[5–8] before calcination was very similar to that of
the effects of the support have not been fully ex- RuACTHNUGTRNEUNG(acac)3. In contrast, a pre-edge peak appeared in
plained. Therefore, the states of Ru species on the the spectra of Ru/CeO2 calcined above 2008C and the
supported catalysts before the catalytic runs were in- intensity increased with an increase in the calcination
vestigated by spectroscopic studies.
temperature. TG and DTA analysis of as-impregnated
Fourier transforms of Ru K-edge extended X-ray Ru/CeO2 showed an exothermic weight decrease at
absorption fine structure (EXAFS) spectra of the sup- around 2008C (see Figure S6 in Supporting Informa-
ported Ru catalysts calcined at 4008C are shown in tion). In DRIFT spectra of Ru/CeO2 calcined above
Figure 1 (a). The peaks at 2.0–4.0 ꢁ due to a second 2008C, a peak due to Ru-oxo species was observed,
coordination sphere in the spectrum of Ru/CeO2 were while such a peak was not seen for catalysts calcined
very weak, presumably because of the presence of below 1508C (see Figure S7 in Supporting Informa-
highly dispersed Ru species on CeO2. On the other tion). These results indicated the presence of a
hand, the spectra of Ru catalysts on SiO2, Al2O3 and RuACHTUNRGTENNUG(acac)3 or RuACHTUNGTREN(NNGU acac)3-like species on uncalcined Ru/
TiO2 closely resembled that of crystalline RuO2. The CeO2 and the formation of a distorted Ru(IV)-oxo
dispersions of Ru species on these supports as esti- species after the combustion of acetylacetonato li-
mated from the EXAFS study are consistent with the gands. Figure 2 (b) shows the yield of 3a from the re-
XRD measurements (see Figure S3 in Supporting In- action at 1108C for 1 h with Ru/CeO2 calcined at vari-
formation). Ru species on MgO seem to be highly dis-
persed but were not effective for the catalytic reac-
tion. This indicates that a characteristic feature other
than the dispersion of Ru species must be important
for the catalysis, as described below, The X-ray ab-
sorption near-edge structure (XANES) spectra of Ru
catalysts supported on SiO2, Al2O3 and TiO2 are
almost identical to that of rutile-type RuO2 [Figure 1
(b)]. In contrast, the coordination environment of Ru
species on CeO2 was distinctly different: a pre-edge
peak appeared at 22110 eV, indicating the formation
of Ru(IV) species in a distorted coordination environ-
ment on CeO2.[18] A pre-edge peak was observed in
the XANES spectrum of Ru/ZrO2 (see Figure S5 in
Supporting Information). Furthermore, the diffuse re-
flectance infrared Fourier transformed (DRIFT) spec-
trum of Ru/CeO2 showed a characteristic peak at
980 cmÀ1 that could be assigned to the Ru=O vibra-
Figure 2. (a) Ru K-edge XANES spectra and (b) the catalyt-
tion mode,[18] while such a peak was not observed for
ic activities of Ru/CeO2 calcined at various temperatures
RuO2 and Ru catalysts supported on SiO2, Al2O3, (the reactions were performed at 1108C for 1 h).
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while calcination above 7008C decreased the catalyst
activity.
To investigate the state of Ru species during the re-
action, XANES and DRIFT spectra of the sample
after the treatment of Ru/CeO2-600cal with HCO2Na
in DMA at 1108C for 15 min were obtained as shown
in Figure 3. The absorption-edge of the XANES spec-
trum of the treated catalyst shifted to a lower energy,
while Ru metal showed a completely different spec-
trum. Moreover, the peak due to Ru-oxo species in
the DRIFT spectrum disappeared after the treatment.
These results indicate that the Ru(IV) species are re-
duced to low-valent Ru species, but not to Ru metal,
with a loss of a Ru=O bond at the initial stage of the
reaction.
Considering the combined results of the catalytic
reactions and spectroscopic analyses, the critical
reason for the specific catalysis of Ru/CeO2 or Ru/
ZrO2 is considered to be the formation of Ru(IV)-
oxo species having a distorted coordination environ-
Figure 3. (a) Ru K-edge XANES and (b) DRIFT spectra of
Ru/CeO2-600 cal before and after treatment in DMA.
ous temperatures. Ru/CeO2 before calcination did not ment on the supports. The Ru(IV)-oxo species trans-
show catalytic activity, and the reaction with Ru/ form into catalytically-active low-valent Ru species
CeO2-150cal resulted in a low yield of 3a. On the under appropriate reaction conditions.
other hand, the reactions with the catalysts calcined
The results of the coupling reaction using Ru/CeO2-
above 3008C proceeded efficiently, and Ru/CeO2- 600cal are summarized in Table 2. The reaction of 1a
600cal showed the highest activity. There was a good with 2a at 1108C was completed within 2 h (entry 1).
correlation between the catalytic activity and the in- After the reaction, the catalyst could be easily sepa-
tensity of the pre-edge peaks in XANES spectra, rated from the reaction mixture by centrifugation.
Table 2. Reaction of internal alkynes with acrylate derivatives catalyzed by Ru/CeO2.
Entry
R1
R2
R3
Time [h]
3
Yield [%][a]
A:B
1
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Me
Me
Me
Me
Me
Et
n-Bu
t-Bu
Me
Me
Me
2
2
2
3
4
4
4
2
6
24
4
3a
3a
3a
3a
3a
3b
3c
3d
3e
3f
3g
98[b] (93:7)
98[b] (93:7)
95[b] (93:7)
94[b] (93:7)
98[b] (95:5)
86 (99:1)
87 (94:6)
92 (85:15)
73 (99:1)
43 (72:28)
–
–
–
–
–
–
–
–
2[c]
3[d]
4[e]
5[f]
6[f]
7
8[g]
9
4-MeO-C6H4
4-Cl-C6H4
Ph
4-MeO-C6H4
4-Cl-C6H4
Me
–
–
10
11[f]
76 (3gA=95:5, 3gB=95:5)
87:13
[a]
Isolated yield (g,d-Z/E-selectivities in parentheses).
Determined by GLC.
Recycle from entry 1 (244 mg as Ru/CeO2).
Recycle from entry 2 (236 mg as Ru/CeO2).
Recycle from entry 3 (226 mg as Ru/CeO2).
Reaction at 1008C.
[b]
[c]
[d]
[e]
[f]
[g]
Reaction at 1208C.
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Intermolecular Coupling of Alkynes with Acrylates by Recyclable Oxide-Supported Ruthenium Catalysts
Scheme 2. Reactions of terminal alkynes with methyl acrylate catalyzed by Ru/CeO2.
The resulting solid was washed and then calcined at sodium formate did not give 1,3-dienes. Various ter-
6008C to recover Ru/CeO2 for reuse. As shown in en- minal alkynes and 1,3-enyne could be used in the
tries 2–4, the solid catalyst could be recycled at least present catalytic system.
three times without a significant loss of the activity.
Several ruthenium complexes have been reported
The reaction was completed within 4 h even at 1008C to catalyze the intermolecular couplings of two differ-
(entry 5). Ethyl, butyl and tert-butyl acrylates also ent alkenes.[11e,21] The coupling reactions of norbor-
gave the corresponding dienes in high yields (en- nene with acrylates proceeded in the presence of Ru/
tries 6–8). As an unsymmetrical internal alkyne, 1- CeO2 catalysts together with sodium formate to give
phenyl-1-propyne (1b) was examined and the corre- exo-alkenylated norbornanes in good yields with high
sponding dienes were obtained as a mixture of re- E selectivities (>40:1) (Scheme 3).
gioisomers (entry 11). The reaction with aliphatic in-
ternal alkynes, such as 4-octyne, gave a complex mix- kynes with alkenes have been proposed under homo-
ture of unidentified compounds. geneous catalysis conditions. The first is a pathway
Several mechanisms for the coupling reaction of al-
Note that the amounts of Ru species that leached via the formation of a ruthenacycle intermediate
into the solution after the reactions in entries 1 and 5 (Scheme 4, path A)[11a,f] and the second involves the
were only 0.00105 mmol and 0.00033 mmol (2.1% and generation of Ru hydride species, followed by the suc-
À
0.66% of Ru species in the fresh catalyst), respective- cessive insertion of alkyne and alkene to Ru H or
[11e,22,23]
À
ly. On the other hand, hot filtration of solid Ru cata- Ru C bonds (path B).
Although a mechanism
2
À
lysts after the reaction for 45 min did not completely that includes the activation of an sp C H bond of ac-
stop the reaction, which suggests that not only Ru rylate has also been proposed,[11g,12c] the absence of
species on the solid surface but also a very small the formation of a cis isomer at the a,b position of
amount of soluble Ru species are responsible for the dienes and no isomerization in the course of the reac-
2
À
reaction (See Figure S1 in Supporting Information). tion suggest that the pathway via sp C H bond acti-
More detailed studies on the state of active Ru spe- vation seems to be unlikely in the present case. The
cies are in progress.
reaction of deuterium-labeled phenylacetylene with
The coupling reactions of terminal alkynes with ac- methyl acrylate gave the D-scrambled 1,3-diene (see
À
rylate by the Ru/CeO2 catalyst were also examined Supporting Information), which suggests that Ru H
(Scheme 2). The addition of lithium iodide enhanced species are generated during the reaction. On the
the yield of 5,[11d] while the reaction in the absence of other hand, the predominant 1,2-migration of deuteri-
Scheme 3. Ru/CeO2-catalyzed coupling of norbornene with acrylates.
Adv. Synth. Catal. 2011, 353, 2837 – 2843
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Scheme 4. Possible mechanisms for the coupling of alkynes with acrylates by low-valent Ru species generated from Ru(IV)-
oxo species.
tion and concentrated under reduced pressure. The products
were isolated by a column chromatography (hexane:ethyl
acetate=10:1, v/v) to give the product 3b as a white solid;
yield: 239 mg (86%).
um was not observed. This ruled out the formation of
Ru-vinylidene species[11b] in the reaction of terminal
alkynes. Although path A cannot be completely ex-
cluded because of the formation of non-hydride low-
valent Ru species from Ru dihydride species,[17a] it is
highly possible that Ru(IV)-oxo species in the pres-
ence of HCO2Na are transformed into Ru hydride
species, which catalyze the reaction via path B.
Acknowledgements
This research was supported by a Grant-in-Aid for Scientific
Research (No. 21360393) from Ministry of Education, Cul-
ture, Sports, Science and Technology, Japan. This work has
been performed with the approval of Spring-8 (Proposal No.
2009B1356). K. W. acknowledges financial support from the
Takahashi Industrial and Economic Foundation.
Conclusions
In summary, we have described a highly efficient cou-
pling of alkynes with acrylates by Ru/CeO2 or Ru/
ZrO2 catalysts in the presence of sodium formate. The
coupling of two different alkenes was also realized
with this catalytic system. Spectroscopic studies sug-
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