Nickel nanoparticle-catalyzed carboxylation of unsaturated hydrocarbon with CO2 using sulfur-modified Au-supported nickel material

Article abstract of DOI:10.1246/cl.190650

A hydrocarboxylation reaction of alkyne or styrene derivatives with CO₂ proceeded smoothly by using an air-stable nano-sized nickel catalyst supported on sulfur-modified gold (SANi), giving functionalized acrylic acids and phenylpropionic acids including an anti-inflammatory drug, Flurbiprofen. Notably, SANi could be recycled several times without a significant decrease of the yield.

Full text of DOI:10.1246/cl.190650

CL-190650
Received: August 21, 2019 | Accepted: September 10, 2019 | Web Released: September 20, 2019
Nickel Nanoparticle-catalyzed Carboxylation of Unsaturated Hydrocarbon
with CO2 Using Sulfur-modified Au-supported Nickel Material
Takahisa Taniguchi,1 Nozomi Saito,1,³ Ryohei Doi,1 Arato Kimoto,1 Naoyuki Hoshiya,1 Katsumasa Fujiki,2
Satoshi Shuto,1 Hiromichi Fujioka,2 Mitsuhiro Arisawa,*2 and Yoshihiro Sato*1
1Faculty of Pharmaceutical Sciences, Hokkaido University, Kita-12, Nishi-6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
2Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan
E-mail: arisaw@phs.osaka-u.ac.jp (M. Arisawa), biyo@pharm.hokudai.ac.jp (Y. Sato)
A
hydrocarboxylation reaction of alkyne or styrene
derivatives with CO2 proceeded smoothly by using an air-stable
nano-sized nickel catalyst supported on sulfur-modified gold
(SANi), giving functionalized acrylic acids and phenylpropionic
acids including an anti-inflammatory drug, Flurbiprofen.
Notably, SANi could be recycled several times without a
significant decrease of the yield.
Scheme 1. Plan for carboxylation using SANi. Ar = aromatic
ring, R = aryl or alkyl group.
Keywords: Carboxylation
| Carbon dioxide fixation |
Nickel nanoparticle
catalysts including Ni NPs can efficiently promote hydrogena-
tion of CO2 (e.g. Sabatier reaction).10 Thus, we focused on
carboxylation of carbon-carbon multiple bonds with CO2 using
SANi. Recently, Ma and Rovis independently reported Ni-
catalyzed hydrocarboxylation of alkynes8 or styrenes9 with CO2
using Ni(cod)2 or Ni(acac)2 as a catalyst and Et2Zn as a reducing
reagent. We chose these reaction systems for the evaluation of
catalytic behavior of SANi for carboxylation of C-C multiple
bonds with CO2 (Scheme 1).
First, diphenylacetylene (1a, 0.25 mmol) was reacted with
Et2Zn (1 M in toluene, 0.75 mL, 0.75 mmol) and SANi (100
mesh, 12 mm © 14 mm, immobilized Ni: ca. 509 ¯g)5 in ace-
tonitrile (1 mL) at 60 °C by connection of a CO2 balloon to the
reaction vessel (Table 1, run 1). After acidic workup followed
by methylation, the corresponding ester 2a and 5 were obtained
in 59% and 6% yields, respectively. When the reactions were
carried out at a higher temperature (100 °C) in n-butylonitrile
and in DMA instead of in acetonitrile, the yields of 2a slightly
Nanoparticle-supported catalysts have attracted much atten-
tion for the synthesis of fine chemicals and pharmaceuticals due
to their ideal properties such as recyclability and low-leaching of
metal species.1-3 Recently, we have developed a sulfur-modified
Au-supported Pd (SAPd) catalyst that can be easily prepared
through an in situ metal nanoparticle and nanospace simulta-
neous organization (PSSO) method.4 The SAPd showed re-
markable reactivity for Suzuki-Miyaura coupling, Buchwald-
Hartwig amination, C-H bond activation, and double carbon-
ylation with low leaching and good recyclability. In this context,
we have successfully developed a sulfur-modified Au-supported
nickel (SANi) catalyst by a procedure similar to that for SAPd
via the in situ PSSO method (Figure 1).5 Detailed spectroscopic
analyses such as EXAFS and XANES revealed that SANi
consists of self-assembled multilayers of Ni(0) nanoparticles
(NPs) with diameters of ca. 3 nm, and Ni(0) is stable even in air.
Furthermore, SANi was found to be an efficient catalyst for
Kumada-Tamao-Corriu coupling and Negishi coupling with
both a high level of reusability and low-leaching. Based on these
results, we investigated the catalytic behavior of SANi for other
C-C bond-forming reactions.
Table 1. Conditions screening.a)
Carbon dioxide (CO2) is a useful carbon source in organic
chemistry because it is abundant, cheap, and relatively non-
toxic. It is well known that a zero-valent-nickel complex can
activate CO2, and various homogeneous zero-valent nickel
complexes have been used for carboxylation of carbon-carbon
multiple bonds with CO2.6-10 In contrast, carboxylation reaction
using CO2 as a C1 source by heterogeneous Ni catalysts still
remains relatively unexplored, although it is known that
yield (%)c)
b)
run solvent CO2
temp.
2a
3a
4
5
SM rec.
1
2
3
MeCN
nPrCN
DMA
B
B
B
60 °C 59
100 °C 72
100 °C 69
®
4
10
®
®
3
6
7
7
31
10
®
4
5
6
7
nPrCN
DMA
dioxane
toluene
S
S
S
S
100 °C 88d)
100 °C 63
100 °C 19
3
3
8
®
®
4
8
®
3
®
®
2
immobilized Ni(0) NPs
27
73
88
easy to handle
recyclable
100 °C
9
3
a)SANi (100 mesh, 12 mm © 14 mm, immobilized Ni: ca. 509
¯g) was used. b)B: balloon, S: sealed tube. c)NMR yield.
d)Isolated yield.
SANi
Figure 1. Sulfur-modified Au-supported Ni catalyst (SANi).
1406 | Chem. Lett. 2019, 48, 1406–1409 | doi:10.1246/cl.190650
© 2019 The Chemical Society of Japan

Table 2. Substrate scope.a)
Scheme 2. Carboxylation of unsymmetrical alkynes. The
optimized conditions shown in Table 2 were applied followed
by HCl and CH2N2 workup.
the alkyne, suggesting that the benzyloxy moiety serves as a
directing group to affect the regioselectivity.
Next, we investigated SANi-catalyzed carboxylation of
styrenes, and the results are summarized in Table 3. It was found
that the reaction of electron-deficient styrene derivatives 6a and
6b under slightly modified conditions from those of the above-
mentioned reaction of alkynes proceeded smoothly to give the
corresponding 2-arylpropionic acid derivatives 7a and 7b in
98% and 68% yields, respectively. Carboxylation of a styrene
carrying C-OTs (Ts = Tosyl) bond, which are usually labile in
the presence of low-valent group 10 metal complexes, interest-
ingly gave the desired product 7c in a good yield. It is
noteworthy that the anti-inflammatory drug Flurbiprofen (7d)
was easily accessible by carboxylation of the corresponding
styrenes with CO2 and Et2Zn.
a)
SANi (100 mesh, 12 mm × 14 mm, immobilized Ni:
ca. 509 µg) was used.
increased to 72% and 69%, respectively (runs 2 and 3). When
the reaction was carried out in a sealed tube under an atmosphere
of CO2, the yield of 2a greatly improved up to 88%, while the
formation of a hydrogenated product 5 was suppressed (run 4).
The use of other solvents including DMA, 1,4-dioxane and
toluene was found to be not effective in this reaction (runs 5-7).
With the optimal reaction conditions in hand, we next
examined the substrate scope of this SANi-catalyzed carboxyla-
tion of alkynes (Table 2). The reaction of symmetrical dialkyl
substituted alkynes such as 4-octyne only gave a trace amount of
the desired carboxylated product. On the other hand, the reaction
of symmetrical diaryl alkynes proceeded, giving the correspond-
ing carboxylated methyl esters in moderate to high yields
with high cis selectivity (2b-2g). In the reaction of 1h (R = 2-
naphthyl), the corresponding carboxylated product 2h was
obtained in 83% yield along with trans-isomer 3h in 10% yield.
When the reaction of aryl-phenethyl-substituted alkyne 1i as
an unsymmetrical alkyne was carried out, 60% of the carboxyl-
ated product was obtained as a 1/1.2 regioisomer mixture
(Scheme 2, eq 1). On the other hand, in the reaction of sub-
strates having an oxygen functionality in the tether, it was found
that regioselective carboxylation occurred. Thus, the reaction of
1j under optimal conditions gave products of 2ja and 2jb in a
total yield of 88% in a ratio of 3.2/1. Also, the reaction of 1k
showed the same tendency, producing 2ka and 2kb in a total
yield of 91% in a ratio of 9.1/1. It is noteworthy that the major
isomers in both reactions of 1j and 1k are always produced via
carboxylation at the carbon near the oxygen functionality in
Table 3. Carboxylation of styrene derivatives.a)
a)
SANi (100 mesh, 12 mm
× 14 mm,
immobilized Ni: ca. 509 µg) was used. b) Isolated
after methylation with CH2N2.
Chem. Lett. 2019, 48, 1406–1409 | doi:10.1246/cl.190650
© 2019 The Chemical Society of Japan | 1407

Table 4. Reusability of SANi for carboxylation of alkyne
amount of
Ni (¯mol)c)
conc. of
Ni (ppm)
cycle
yield (%)a),b)
1st
2nd
3rd
74
79
75
0.11
0.063
0.073
3.8
2.1
2.5
average of
3 cycles
76
0.083
2.8
Figure 2. Reusability of SANi for carboxylation of styrene.
a)Yields were determined by HPLC analysis. b)The yield of
each cycle was calculated by the average of three reactions
under the same conditions. c)The amount of Ni was determined
by ICP-MS.
potential activity of Ni NPs for C-C bond formation reactions
beyond cross-coupling reaction systems.13 It is thought that these
SANi-catalyzed hydrocarboxylations proceed via a hydrozinca-
tion process which had been reported by Ma8 and Rovis9 by
using a conventional nickel complex. Further studies using
SANi as a platform of Ni NPs including mechanistic studies are
in progress.
We turned our attention to the reusability of SANi in the
reaction of diphenylacetylene. After the first reaction of
diphenylacetylene under optimal conditions, SANi was removed
from the reaction mixture and reused in the next reaction. As a
result, it was found that SANi could be used three times without
a significant decrease of yield. On the basis of the results of ICP-
MS analysis of each cycle of the reaction mixture shown in
Table 4, it was revealed that the amount of Ni leached was 0.07-
0.11 ¯mol, which is approximately 1% of the total amount of Ni
on SANi, and that the concentration of Ni in the reaction mixture
was 2.1-3.8 ppm.11
We also checked reusability of SANi for carboxylation of
styrene derivatives. After carboxylation of 6a was performed
with SANi, which delivered desired product in 98%, the SANi
was removed before workup. When this SANi was reused as
catalyst for carboxylation of 6a, the yield dropped to 25%. We
thought that under carboxylation conditions for styrenes using
highly polar solvent DMA, the amount of leaching Ni would be
too large to withstand repetitious usage.12 Thus, we assumed that
removal of SANi from the reaction mixture after leaching Ni
NPs precludes SANi from full consumption of active Ni. To a
reaction vessel was charged SANi, styrene 6a and DMA and
the mixture was heated at 80 °C for 4 h to complete leaching
(Figure 2). After quick removal of SANi, the vessel was
attached to CO2 balloon and ZnEt2 was added. After 24 h
stirring, 95% of 7a was obtained. Repeating the same sequence
delivered 7a in 84%. Finally, SANi was used as catalyst without
removal for 24 h to give the carboxylated product in 60%.
Although further investigation to find optimized condition for
repetitious use is required, we successfully demonstrated
reusability of SANi for carboxylation of styrenes.
This work was supported by several funds and grants as
follows; Grants-in-Aids from JSPS for Scientific Research (B)
(Grant No. 26293001) (for Y.S.) and for Precisely Designed
Catalysts with Customized Scaffolding (Grant No. JP
18H04260), T15K149760, and T15KT00630 (for M.A.);
ACT-C (Grant No. JPMJCR12YM) from JST (for Y.S. and
M.A.); Platform Project for Supporting Drug Discovery and
Life Science Research (Basis for Supporting Innovative Drug
Discovery and Life Science Research (BINDS)) from AMED
(Grant No. JP19am0101084) (for M.A.); Research Fellowship
for Young Scientists (Grant No. 16J0399506) (for T.T.).
Supporting Information is available on https://doi.org/
10.1246/cl.190650.
References and Notes
³
Present address: Meiji Pharmaceutical University, 2-522-1
Noshio, Kiyose, Tokyo 204-8588, Japan
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Chem. Lett. 2019, 48, 1406–1409 | doi:10.1246/cl.190650
© 2019 The Chemical Society of Japan | 1409