Synthesis of Trisubstituted Acrylic Acids through Nickel-Catalyzed Carbomagnesiation of Alkynes and Carbon Dioxide Fixation

Article abstract of DOI:10.1002/ejoc.201801364

A nickel-catalyzed synthesis of trisubstituted acrylic acids from alkynes, Grignard reagents, and CO₂ is reported. The reaction proceeds through carbomagnesiation of the alkyne with Grignard reagent followed by carboxylation with CO₂ under mild reaction conditions in short time. Various unsymmetrical alkynes were transformed into the corresponding acid products in good yields with high stereoselectivity.

Full text of DOI:10.1002/ejoc.201801364

A Journal of
Accepted Article
Title: Synthesis of Trisubstituted Acrylic Acids via Nickel-Catalyzed
Carbomagnesiation of Alkynes and Carbon Dioxide Fixation
Authors: Chen-Hsun Hung, Rajagopal Santhoshkumar, Yu-Che
Chang, and Chien-Hong Cheng
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201801364
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10.1002/ejoc.201801364
European Journal of Organic Chemistry
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Synthesis of Trisubstituted Acrylic Acids via Nickel-Catalyzed
Carbomagnesiation of Alkynes and Carbon Dioxide Fixation
Chen-Hsun Hung, Rajagopal Santhoshkumar, Yu-Che Chang, and Chien-Hong Cheng*[a]
Dedication ((optional))
Abstract: A nickel-catalyzed synthesis of trisubstituted acrylic acids
from alkynes, Grignard reagents, and CO2 was demonstrated. The
reaction proceeds through carbomagnesiation of the alkyne with
Grignard reagent followed by carboxylation with CO2 under mild
reaction conditions in short time. Various unsymmetrical alkynes were
transformed into the corresponding acid products in good yields with
high stereoselectivity.
similar Ni-catalyzed arylative carboxylation of alkynes with
arylmagnesium reagents and CO2.[12]
Introduction
Carbon dioxide (CO2) is a benign, economical and stable one-
carbon (C1) feedstock in organic synthesis.[1] However, since
carbon dioxide is the end product of organic fuel after burning,
and becomes the key molecule responsible for the present global
warming, the fixation of CO2 into useful organic compounds has
attracted great attention in recent years.[2] As CO2 is
thermodynamically stable and kinetically inert but is electron-
deficient, most of the methods developed to activate inert CO2
requiring nucleophilic reagents under harsh reaction conditions.
Thus, effective utilization of CO2 with transition-metal catalysts is
highly attractive.[3] Among the known methods, the reaction of
CO2 with alkynes such as hydrocarboxylation,[4] cyclization,[5] and
carbocarboxylation[6,7] provides efficient routes to construct vinyl
and cyclic carboxyl derivatives. In hydrocarboxylation, metal
hydride or simple alcohol acts as a hydrogen source to afford
unsaturated acrylic acids (Scheme 1a). These methodologies are
beneficial in organic synthesis, however, the synthesis of
trisubstituted acrylic acids has been rarely studied.[7]
Scheme 1. Transformations of alkynes into alkenes and acrylic acids.
Results and Discussion
We initiated the studies using diphenylacetylene 1a (0.20 mmol)
and MeMgBr (0.30 mmol) in the presence of 10 mol% NiBr2·glyme,
and 20 mol% PPh3 in THF at 60°C for 1 h. Then CO2 gas was
introduced to the reaction mixture at 25°C for 30 min to give
carboxylation product 3aa in 82% yield (Table 1, entry 1). Of the
solvents examined, THF was found to be most effective; other
solvents were much less effective (entries 2‒7). Among the nickel
catalysts tested, NiBr2·diglyme (5 mol %) with PPh3 (5 mol %)
gave product 3aa in 88% yield (entries 8‒11). The use of
bidentate ligands such as 1,10-phen, dppe, and bipy gave very
low product yields (entries 12‒14). The reaction is also sensitive
to the temperature: lower product yield was observed with lower
reaction temperature (entries 15‒16).
Encouraged by these results, we started to explore the scope
of alkynes 1a-m for the nickel-catalyzed synthesis of trisubstituted
acrylic acids (Scheme 2). Thus, treatment of symmetrical diaryl
alkynes 1a-e with 2a proceeded well to provide products 3aa-ea
in moderate to excellent yields. The sterically-hindered ortho-
substituted substrate 1f afforded product 3fa in 32% yield.
However, ortho-methoxy substituted alkyne 1g gave 3ga in 83%
yield plausibly due to the ortho-directing effect of the methoxy
group.[13] Naphthyl substituted alkynes 1h-i also furnished the
corresponding acrylic acids 3ha-ia in moderate yields. The
reaction of alkyl(aryl)acetylenes 1j-m with 2a gave highly
regioselective products 3ja-ma in moderate yields. In addition,
double alkyne insertion[14] was also found to give the
corresponding 2,4-dienoic acids 3ja’-la’. The relative yield of
double insertion product decreases as the size of alkyl group
increases probably owing to its steric effect of the alkyl group. The
structure of 3ja’ was unambiguously confirmed by X-ray
crystallography and NOE measurement (see Supporting
Information for details).[15]
In 1978, Jousseaume reported
carbomagnesiation of alkynes to synthesize trisubstituted
alkenes.[8] Recently, Hayashi[9] and others[10] developed
a
nickel-catalyzed
a
transition metal-catalyzed carbomagnesiation of alkynes using
Grignard reagents to produce multi-substituted alkenes (Scheme
1b). Motivated by these results and our continued interest in the
first-row transition metal-catalyzed reactions,[4h,11] we focused on
the development of an appropriate carbometalation method to
synthesize trisubstituted acrylic acids using CO2. Herein, we wish
to report the synthesis of trisubstituted acrylic acids via nickel-
catalyzed carbomagnesiation and subsequent carboxylation
reaction. During our preparation of this manuscript, Xi reported a
[a]
Dr. C.-H. Hung, Dr. R. Santhoshkumar, Y.-C. Chang, and Prof. Dr. C.-
H. Cheng
Department of Chemistry
National Tsing Hua University
Hsinchu, 30013 (Taiwan)
Fax: (+886) 3572-4698
E-mail: chcheng@mx.nthu.edu.tw
http://mx.nthu.edu.tw/~chcheng/
Supporting Information and the ORCID identification number(s) for the
author(s) of this article can be found under http://dx.doi.org/10.1002/
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10.1002/ejoc.201801364
European Journal of Organic Chemistry
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Table 1. Optimization of the reaction conditions[a,b]
Entry
1
Catalyst
Ligand
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
1,10-phen
dppe
bipy
Solvent
THF
Yield (%)[b]
82[c]
11
NiBr2·glyme
NiBr2·glyme
NiBr2·glyme
NiBr2·glyme
NiBr2·glyme
NiBr2·glyme
NiBr2·glyme
NiBr2·diglyme
NiBr2·diglyme
NiCl2·6H2O
NiBr2
2
1,4-dioxane
DME
2-Me THF
furan
DCE
3
3
4
12
5
trace
54
6
7
MeCN
THF
4
76[c]
88[c]
68[c]
trace
59
8
9[d]
10[d]
11[d]
12[d]
13[d]
14[d]
15[e,d]
16[f,d]
17[g]
THF
THF
THF
NiBr2·diglyme
NiBr2·diglyme
NiBr2·diglyme
NiBr2·diglyme
NiBr2·diglyme
NiBr2·diglyme
THF
Scheme 2. The scope of alkynes. The reactions were performed using the
conditions as in footnote g, Table 1. [a] TMEDA (0.025 mmol) instead of PPh3.
[b] Regioisomers were determined by 1H NMR.
THF
trace
17[c]
20
THF
PPh3
PPh3
PPh3
THF
THF
10
THF
81[c]
[a] Reactions were performed using 1a (0.20 mmol), Ni cat. (0.020 mmol), ligand
(0.040 mmol) and MeMgBr (3 M in 2-Me THF, 0.10 mL, 0.30 mmol) in THF (2.0
mL) at 60°C for 1 h, then CO2 in a balloon was introduced to the mixture at 25 °C
with stirring for 30 min. [b] Yields were determined by the 1H NMR integration
method using mesitylene as the internal standard. [c] Isolated yield. [d] Ni cat.
(0.010 mmol) and PPh3 (0.010 mmol) were used. [e] The reaction temperature
is 40°C. [f] The reaction temperature is rt. [g] The reaction was performed using
1a (0.50 mmol), NiBr2·diglyme (0.025 mmol), PPh3 (0.025 mmol) and MeMgBr
(3 M in 2-Me THF, 0.25 mL, 0.75 mmol) in THF (2.0 mL) at 60°C for 1 h.
Next, we focused on unsymmetrical diarylalkynes 1n-r to
investigate the regioselectivity of the reaction (Scheme 3). In
general, the ortho-directing effect,[13] electronic nature,[16] and
steric effect of the unsymmetrical diarylalkynes would control the
regioselectivity of the products. In this context, we observed that
2-methoxyphenyl substituted alkyne 1n gave 3na-α as the major
isomer due to the ortho-directing effect of methoxy group. In
contrast, the electronic donating nature of 4-methoxy substituted
alkyne 1o afforded mainly product 3oa-β. Other substrates 1p
and 1q gave α isomer as the major products in 76% and 47%
yields, respectively. The favourable regioselectivity in the
products form alkynes 1o-q is plausibly due to electronic effect of
the substituent on the phenyl group.[4h,16] Unfortunately, sterically-
hindered alkyne 1r did not give the expected product.
Scheme 3. The scope of unsymmetrical diarylalkynes. The reactions were
performed using conditions as in footnote g, Table 1. [a] α:β ratio were
determined by 1H NMR.
To see the scope of Grignard reagents, we investigated
different alkyl and vinyl Grignard reagents 2b-e for the present
catalytic reaction (Scheme 4). Thus, the reaction of 1b with ethyl
magnesium bromide (2b) afforded the desired product 3bb, albeit
in low yield. The competing β–hydride elimination gave
hydrocarboxylation product 3b in 72% yield and is the major
reaction product. Similarly, n-hexyl and allyl magnesium bromides
2c-d provided the hydrocarboxylation product 3b in 67% and 36%
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10.1002/ejoc.201801364
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were transformed into the corresponding acrylic acids in good
yields with reasonable regioselectivity. Ortho-directing effect,
electronic nature and steric effect of alkynes play a major role in
the regioselectivity. The product, multi-substituted acrylic acid,
could be converted into coumarin derivative for further
applications.
yields, respectively. Nevertheless, vinyl Grignard reagent 2e
furnished vinyl-substituted product 3be in moderate yield.
Scheme 4. The scope of aliphatic Grignard reagents. The Reactions were
performed using the conditions as in footnote g, Table 1. [a] PPh3 (0.050 mmol).
The present catalytic reaction was successfully extended to a
variety of aryl Grignard reagents 2f-q (Scheme 5). However, due
to the low yield for the reaction of phenyl magnesium bromide (2f)
with 1b under the standard reaction conditions, we optimized the
reaction
conditions
by
introducing
N,N,N’,N’-
tetramethylethylenediamine (TMEDA) to the nickel catalyst
system in an attempt to improve the yield. Thus, treatment of 1b
with 2f in the presence of NiBr2·diglyme and TMEDA in toluene
provided the triaryl-substituted acrylic acid 3bf in 78% yield. In a
similar manner, para substituted methyl, methoxy, tert-butyl, and
fluoro phenyl Grignard reagents reacted smoothly with 1b under
the present reaction conditions to afford products 3bg-bj in
moderate to excellent yields. Naphthyl Grignard reagents 2k-l
were also suitable for the present reaction to give acrylic acids
3bk-bl in 73‒74% yields. Likewise, disubstituted aryl Grignard
reagents 2m-p delivered the desired products 3bm-bp in 49‒89%
yields. Finally, sterically-hindered mesityl Grignard reagent 2q
also furnished the acrylic acid product 3bq in 34% yield. It is
noteworthy that the steric effect of alkynes influences the reaction
more than that of the Grignard reagents.
The synthetic method was successfully applied to a gram-scale
synthesis of products 3ba and 3bf in 85% and 92% yields,
respectively (Scheme 6). In the reactions, a lower amount of the
Grignard reagents were used. It is noteworthy that acrylic acid 3bf
could be converted to valuable coumarin derivative 4bf via an
iodine-catalyzed oxidative cyclization under sunlight (Scheme
7).[17]
Scheme 5. Scope of aromatic Grignard reagents. Reactions were performed
using 1b (0.50 mmol), NiBr2·diglyme (0.025 mmol), TMEDA (0.025 mmol) and
ArMgBr (1 M in THF, 0.75 mL, 0.75 mmol) in PhMe (2.0 mL) at 60°C for 1 h,
then CO2 in a balloon was introduced to the mixture at 25 °C with stirring for 30
min, isolated yields. [a] Reaction without ligand. [b] PPh3 (0.050 mmol) instead
of TMEDA. [c]PPh3 (0.025 mmol) instead of TMEDA. [d]THF (2.0 mL) was used
as solvent.
On the basis of literature reports,[4d,8,18] a plausible mechanism
is proposed in Scheme 8 to account for the present reactions. The
reaction is initiated by the reduction of Ni(II) to Ni(0) by the
Grignard reagent. Transmetallation of the Grignard reagent with I
to afford active nickel complex II, coordination of alkyne, followed
by insertion into metal-carbon give IV. Then, transmetallation of
the Grignard reagent with IV delivers V and regenerates II for the
next cycle (path a). Alternatively, alkyne coordinates strongly to
Ni(0) to form Ni complex VI with a formal oxidation state of (II).
Subsequently, transmetallation with Grignard reagent and
reductive elimination provide V (path b). Finally, addition of V to
CO2 and then protonation take place to provide the desired
product 3.
Scheme 6. Gram-scale synthesis of trisubstituted acrylic acids.
Conclusions
In conclusion, we have developed an efficient nickel-catalyzed
carbomagnesiation and subsequent carboxylation reaction from
alkynes, Grignard reagents, and CO2 under mild reaction
conditions in short reaction time. Various unsymmetrical alkynes
Scheme 7. Synthesis of coumarin derivative.
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10.1002/ejoc.201801364
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= 8.0 Hz, 2 H), 7.00 (d, J = 8.0 Hz, 2 H), 2.28 (s, 3 H), 2.15‒2.09 (m, 1 H),
1.87 (s, 3 H), 1.61 (d, J = 13.2 Hz, 2 H), 1.51 (d, J = 12.4 Hz, 1 H), 1.40‒
1.27 (m, 4 H), 1.11‒1.02 (m, 1 H), 0.96‒0.87 (m, 2 H) ppm; 13C NMR (100
MHz, d6-DMSO): δ = 170.0 (CO), 146.9 (C), 135.9 (C), 134.9 (C), 130.3
(C), 128.7 (2 CH), 128.6 (2 CH), 41.9 (CH), 29.8 (2 CH2), 25.6 (2 CH2),
25.3 (CH2), 20.7 (CH3), 15.2 (CH3) ppm; HRMS (EI+): calcd. for C17H22O2
258.1620, found 258.1615; IR (KBr): ṽ = 2931, 2854, 1673, 1604, 1403,
1249, 933, 740 cm-1.
(E)-2-(2-Methoxyphenyl)-3-phenylbut-2-enoic acid (3na-α): White solid;
1H NMR (400 MHz, d6-DMSO): δ = 12.26 (s, 1 H), 7.10‒7.02 (m, 4 H),
6.99‒6.95 (m, 2 H), 6.83 (d, J = 7.6 Hz, 1 H), 6.62 (dd, J = 7.6 Hz, J = 2.0
Hz, 1 H), 6.58‒6.54 (m, 1 H), 3.67 (s, 3 H), 2.36 (s, 3 H) ppm; 13C NMR
(100 MHz, d6-DMSO): δ = 169.4 (CO), 157.2 (C), 146.4 (C), 142.9 (C),
131.9 (CH), 129.1 (C), 128.1 (C), 128.1 (CH), 127.7 (2 CH), 127.6 (2 CH),
126.8 (CH), 119.7 (CH), 110.6 (CH), 55.2 (CH3), 22.6 (CH3) ppm; HRMS
(EI+): calcd. for C17H16O3 268.1099, found 268.1096.
(E)-3-(4-Methoxyphenyl)-2-phenylbut-2-enoic acid (3oa-β): White solid;
1H NMR (400 MHz, d6-DMSO): δ = 12.72 (s, 1 H), 7.15‒7.05 (m, 3 H),
6.97‒6.94 (m, 4 H), 6.72‒6.68 (m, 2 H), 3.65 (s, 3 H), 2.23 (s, 3 H) ppm;
13C NMR (100 MHz, d6-DMSO): δ = 170.5 (CO), 158.1 (C), 140.5 (C),
137.7 (C), 133.5 (C), 132.0 (C), 129.6 (2 CH), 129.5 (2 CH), 127.8 (2 CH),
126.5 (CH), 113.3 (2 CH), 54.9 (CH3), 22.8 (CH3) ppm; HRMS (EI+): calcd.
for C17H16O3 268.1099, found 268.1096.
Scheme 8. A plausible catalytic cycle.
Experimental Section
General procedure for the synthesis of acrylic acid 3: A Schlenk tube
containing alkynes 1 (0.50 mmol), NiBr2·diglyme (8.9 mg, 0.025 mmol) and
PPh3 (6.6 mg, 0.025 mmol) was evacuated and purged with nitrogen gas
three times. Then dried THF (2.0 mL) and Grignard reagent (0.75 mmol)
were added into the mixture in sequence. The reaction mixture was
allowed to stir at 60 °C for 1 h. Next, the mixture was cooled to room
temperature, nitrogen was removed by vacuum, and then CO2 balloon was
inserted. Later, the reaction stirred at 25°C for another 30 min. When the
reaction was completed, the mixture was diluted with EtOAc, quenched
with 20% HCl(aq) (2 mL) and extracted with EtOAc (3 × 10 mL). The
combined organic phase was dried over MgSO4, filtered through a Celite
pad, and the solvents were removed in vacuum to give the crude product,
which was purified by column chromatography using ethyl acetate/n-
hexane system to afford multi-substituted acrylic acid 3.
(E)-2,3-Di-p-tolylpent-2-enoic acid (3bb): White solid; m.p. 188‒191°C;
1H NMR (400 MHz, d6-DMSO): δ = 12.68 (s, 1 H), 6.98 (d, J = 8.0 Hz, 2
H), 6.91 (d, J = 8.0 Hz, 2 H), 6.90 (d, J = 8.0 Hz, 2 H), 6.81 (d, J = 8.4 Hz,
2 H), 2.58 (q, J = 7.2 Hz, 2 H), 2.20 (s, 3 H), 2.16 (s, 3 H), 0.87 (t, J = 7.6
Hz, 3 H) ppm; 13C NMR (100 MHz, d6-DMSO): δ = 170.6 (CO), 145.0 (C),
136.7 (C), 135.9 (C), 135.6 (C), 134.2 (C), 131.8 (C), 129.1 (2 CH), 128.7
(2 CH), 128.6 (2 CH), 128.3 (2 CH), 29.2 (CH2), 20.6 (CH3), 20.5 (CH3),
12.7 (CH3) ppm; HRMS (FD+): calcd. for C19H20O2 280.1463, found
280.1462; IR (KBr): ṽ = 2969, 2869, 1681, 1596, 1511, 1403, 1272, 817,
725 cm-1.
(E)-2,3-Di-p-tolylpenta-2,4-dienoic acid (3be): White solid; m.p. 158‒
161°C; 1H NMR (400 MHz, d6-DMSO): δ = 13.05 (s, 1 H), 7.04 (d, J = 8.0
Hz, 2 H), 6.99 (dd, J = 17.2 Hz, J = 10.8 Hz, 1 H), 6.92 (d, J = 8.4 Hz, 2 H),
6.88 (d, J = 8.4 Hz, 2 H), 6.84 (d, J = 8.0 Hz, 2 H), 5.34 (dd, J = 10.8 Hz, J
= 1.6 Hz, 1 H), 4.84 (dd, J = 17.2 Hz, J = 1.6 Hz, 1 H), 2.23 (s, 3 H), 2.16
(s, 3 H) ppm; 13C NMR (100 MHz, d6-DMSO): δ = 170.1 (CO), 140.1 (C),
136.6 (CH), 136.2 (C), 136.2 (C), 135.0 (C), 133.6 (C), 133.4 (C), 129.9 (2
CH), 128.9 (2 CH), 128.6 (2 CH), 128.3 (2 CH), 120.3 (CH2), 20.7 (CH3),
20.6 (CH3) ppm; HRMS (EI+): calcd. for C19H18O2 278.1307, found
278.1295; IR (KBr): ṽ = 3463, 3023, 2923, 1689, 1504, 1403, 1265, 1025,
925, 817 cm-1.
(E)-2,3-Diphenylbut-2-enoic acid (3aa): White solid; m.p. 185‒187°C; 1H
NMR (400 MHz, d6-DMSO): δ = 12.80 (s, 1 H), 7.16‒7.07 (m, 6 H), 7.04‒
7.02 (m, 2 H), 6.96‒6.94 (m, 2 H), 2.26 (s, 3 H) ppm; 13C NMR (100 MHz,
d6-DMSO): δ = 170.2 (CO), 141.6 (C), 141.0 (C), 137.3 (C), 132.6 (C),
129.4 (2 CH), 128.2 (2 CH), 127.9 (2 CH), 127.7 (2 CH), 126.9 (CH), 126.6
(CH), 22.8 (CH3) ppm; HRMS (EI+): calcd. for C16H14O2 238.0994, found
238.0987; IR (KBr): ṽ = 3417, 2962, 1673, 1589, 1403, 1272 cm-1.
(E)-2,3-Di-m-tolylbut-2-enoic acid (3ea): White solid; m.p. 108‒110°C;
1H NMR (400 MHz, d6-DMSO): δ = 12.75 (s, 1 H), 7.03‒6.95 (m, 2 H),
6.93‒6.88 (m, 3 H), 6.82 (s, 1 H), 6.77 (d, J = 7.6 Hz, 1 H), 6.71 (d, J = 7.6
Hz, 1 H), 2.23 (s, 3 H), 2.14 (s, 3 H), 2.12 (s, 3 H) ppm; 13C NMR (100
MHz, d6-DMSO): δ = 170.4 (CO), 141.5 (C), 140.2 (C), 137.1 (C), 136.9
(C), 136.6 (C), 132.5 (C), 129.7 (CH), 128.7 (CH), 127.7 (CH), 127.5 (CH),
127.5 (CH), 127.2 (CH), 126.7 (CH), 125.4 (CH), 22.8 (CH3), 20.9 (CH3),
20.8 (CH3) ppm; HRMS (EI+): calcd. for C18H18O2 266.1307, found
266.1298; IR (KBr): ṽ = 3494, 2915, 1689, 1604, 1403, 1249 cm-1.
(Z)-3-(4-(tert-Butyl)phenyl)-2,3-di-p-tolylacrylic acid (3bi): White solid;
m.p. 220‒222°C; 1H NMR (400 MHz, d6-DMSO): δ = 12.59 (s, 1 H), 7.34
(d, J = 8.4 Hz, 2 H), 7.12 (d, J = 8.4 Hz, 2 H), 6.99 (d, J = 8.4 Hz, 2 H),
6.96 (d, J = 10.0 Hz, 2 H), 6.92 (d, J = 8.4 Hz, 2 H), 6.79 (d, J = 8.0 Hz, 2
H), 2.21 (s, 3 H), 2.20 (s, 3 H), 1.27 (s, 9 H) ppm; 13C NMR (100 MHz, d6-
DMSO): δ = 171.1 (CO), 150.0 (C), 141.7 (C), 139.2 (C), 137.8 (C), 136.5
(C), 136.3 (C), 134.6 (C), 133.8 (C), 130.2 (2 CH), 129.1 (2 CH), 128.7 (2
CH), 128.6 (2 CH), 128.5 (2 CH), 124.8 (2 CH), 34.2 (C), 31.0 (3 CH3),
20.6 (2 CH3) ppm; HRMS (EI+): calcd. for C27H28O2 384.2089, found
384.2079; IR (KBr): ṽ = 3694, 3023, 2954, 2869, 1689, 1589, 1511, 1403,
1272, 809 cm-1.
3-Methyl-2-phenylbut-2-enoic acid (3ja): White solid; m.p. 158‒160°C;
1H NMR (400 MHz, d6-DMSO): δ = 12.32 (s, 1 H), 7.33 (t, J = 7.2 Hz, 2 H),
7.25 (t, J = 7.2 Hz, 1 H), 7.13 (d, J = 6.8 Hz, 2 H), 2.03 (s, 3 H), 1.61 (s, 3
H) ppm; 13C NMR (100 MHz, d6-DMSO): δ = 169.4 (CO), 141.7 (C), 138.2
(C), 130.7 (C), 129.1 (2 CH), 128.0 (2 CH), 126.7 (CH), 22.5 (CH3), 22.2
(CH3) ppm; HRMS (EI+): calcd. for C11H12O2 176.0837, found 176.0832; IR
(KBr): ṽ = 3471, 1681, 1619, 1411, 1265, 1095 cm-1.
3,4-di-p-tolyl-2H-chromen-2-one (4bf): White solid; 1H NMR (400 MHz,
CDCl3): δ = 7.49 (td, J = 7.2 Hz, J = 1.6 Hz, 1 H), 7.38 (dd, J = 8.4 Hz, J =
0.8 Hz, 1 H), 7.21 (dd, J = 8.0 Hz, J = 1.6 Hz, 1 H), 7.14 (td, J = 7.2 Hz, J
= 1.2 Hz, 1 H), 7.10 (d, J = 7.6 Hz, 2 H), 7.01‒6.95 (m, 6 H), 2.32 (s, 3 H),
2.24 (s, 3 H) ppm; 13C NMR (100 MHz, CDCl3): δ = 161.5 (CO), 153.1 (C),
151.3 (C), 138.0 (C), 137.2 (C), 131.6 (C), 131.1 (CH), 130.9 (C), 130.3 (2
CH), 129.2 (2 CH), 128.9 (2 CH), 128.4 (2 CH), 127.7 (CH), 126.8 (C),
123.9 (CH), 120.7 (C), 116.6 (CH), 21.2 (CH3), 21.2 (CH3) ppm; HRMS
(FD+): calcd. for C23H18O2 326.1307, found 326.1310.
(Z)-3,5-Dimethyl-2,4-diphenylhexa-2,4-dienoic acid (3ja’): White solid;
m.p. 115‒117°C; 1H NMR (400 MHz, d6-DMSO): δ = 12.35 (s, 1 H), 7.42
(d, J = 6.8 Hz, 2 H), 7.39‒7.29 (m, 5 H), 7.27‒7.21 (m, 3 H), 1.85 (s, 3 H),
1.64 (s, 3 H), 1.49 (s, 3 H) ppm; 13C NMR (100 MHz, d6-DMSO): δ = 169.9
(CO), 141.4 (C), 139.7 (C), 137.3 (C), 136.6 (C), 133.3 (C), 129.6 (2 CH),
129.0 (2 CH), 128.7 (C), 128.2 (2 CH), 127.8 (2 CH), 127.2 (CH), 126.5
(CH), 21.9 (CH3), 21.5 (CH3), 19.4 (CH3) ppm; HRMS (EI+): calcd. for
C20H20O2 292.1463, found 292.1458; IR (KBr): ṽ = 3694, 2985, 1689, 1596,
1403, 1295, 1072 cm-1.
Acknowledgements
We thank the Chang Chun Petrochemical Company, Chang Chun
Plastics Company and Ministry of Science and Technology of the
(E)-3-Cyclohexyl-2-(p-tolyl)but-2-enoic acid (3ma): White solid; m.p.
188‒190°C; 1H NMR (400 MHz, d6-DMSO): δ = 12.28 (s, 1 H), 7.13 (d, J
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Republic of China (MOST-105-2622-8-007-009 and MOST-105-
2633-M-007-003) for support of this research.
Cheng, Angew. Chem. Int. Ed. 2009, 48, 2192-2195; d) P. Gandeepan, K.
Parthasarathy, T. H. Su, C. H. Cheng, Adv. Synth. Catal. 2012, 354, 457-
468; e) R. Santhoshkumar, S. Mannathan, C. H. Cheng, Org. Lett. 2014,
16, 4208-4211.
Keywords: Nickel • Alkynes • Carbon Dioxide • Acrylic Acids •
[12]. S. Wang, C. Xi, Org. Lett. 2018, 20, 4131-4134.
Carbomagnesiation
[13]. M. Alami, F. Liron, M. Gervais, J. F. Peyrat, J. D. Brion, Angew. Chem. Int.
Ed. 2002, 41, 1578-1580.
[1]. a) H. Arakawa, M. Aresta, J. N. Armor, M. A. Barteau, E. J. Beckman, A.
T. Bell, J. E. Bercaw, C. Creutz, E. Dinjus, D. A. Dixon, K. Domen, D. L.
DuBois, J. Eckert, E. Fujita, D. H. Gibson, W. A. Goddard, D. W. Goodman,
J. Keller, G. J. Kubas, H. H. Kung, J. E. Lyons, L. E. Manzer, T. J. Marks,
K. Morokuma, K. M. Nicholas, R. Periana, L. Que, J. Rostrup-Nielson, W.
M. H. Sachtler, L. D. Schmidt, A. Sen, G. A. Somorjai, P. C. Stair, B. R.
Stults, W. Tumas, Chem. Rev. 2001, 101, 953-996.
[14]. Y. S. Liu, L. J. Wang, L. Deng, J. Am. Chem. Soc. 2016, 138, 112-115.
[15]. CCDC 1555953 (3bf) and 1555954 (3ja') contain the supplementary
crystallographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre.
[16]. a) E. Fager-Jokela, M. Muuronen, M. Patzschke, J. Helaja, J. Org. Chem.
2012, 77, 9134-9147; b) E. Fager-Jokela, M. Muuronen, H. Khaizourane,
A. Vazquez-Romero, X. Verdaguer, A. Riera, J. Helaja, J. Org. Chem.
2014, 79, 10999-11010.
[2]. a) T. Sakakura, J. C. Choi, H. Yasuda, Chem. Rev. 2007, 107, 2365-2387;
b) C. Maeda, Y. Miyazaki, T. Ema, Catal. Sci. Technol. 2014, 4, 1482-
1497; c) Q. Liu, L. P. Wu, R. Jackstell, M. Beller, Nat. Commun. 2015, 6,
5933.
[17]. J. M. Li, H. Y. Chen, D. Zhang-Negrerie, Y. F. Du, K. Zhao, RSC Adv.
2013, 3, 4311-4320.
[18]. a) W. Kaschube, K. R. Porschke, K. Angermund, C. Kruger, G. Wilke,
Chem. Ber. Recl. 1988, 121, 1921-1929; b) J. Terao, H. Watanabe, A.
Ikumi, H. Kuniyasu, N. Kambe, J. Am. Chem. Soc. 2002, 124, 4222-4223.
[3]. a) A. Correa, R. Martin, Angew. Chem. Int. Ed. 2009, 48, 6201-6204; b)
K. Huang, C. L. Sun, Z. J. Shi, Chem. Soc. Rev. 2011, 40, 2435-2452; c)
R. Martin, A. W. Kleij, ChemSusChem 2011, 4, 1259-1263; d) Y. Tsuji, T.
Fujihara, Chem. Commun. 2012, 48, 9956-9964; e) L. Zhang, Z. M. Hou,
Chem. Sci. 2013, 4, 3395-3403; f) D. Y. Yu, S. P. Teong, Y. G. Zhang,
Coord. Chem. Rev. 2015, 293, 279-291; g) M. Ruben, T. Andreu, J.-H.
Francisco, B. Marino, M. Toni, Angew. Chem. Int. Ed., 2018,
doi:10.1002/anie.201803186.
[4]. a) S. Saito, S. Nakagawa, T. Koizumi, K. Hirayama, Y. Yamamoto, J. Org.
Chem. 1999, 64, 3975-3978; b) M. Aoki, M. Kaneko, S. Izumi, K. Ukai, N.
Iwasawa, Chem. Commun. 2004, 2568-2569; c) T. Fujihara, T. H. Xu, K.
Semba, J. Terao, Y. Tsuji, Angew. Chem. Int. Ed. 2011, 50, 523-527; d)
S. H. Li, W. M. Yuan, S. M. Ma, Angew. Chem. Int. Ed. 2011, 50, 2578-
2582; e) N. Saito, Z. D. Sun, Y. Sato, Chem. Asian J. 2015, 10, 1170-
1176; f) X. Q. Wang, M. Nakajima, R. Martin, J. Am. Chem. Soc. 2015,
137, 8924-8927; g) M. C. Fu, R. Shang, W. M. Cheng, Y. Fu, ACS Catal.
2016, 6, 2501-2505; h) R. Santhoshkumar, Y. C. Hong, C. Z. Luo, Y. C.
Wu, C. H. Hung, K. Y. Hwang, A. P. Tu, C. H. Cheng, ChemCatChem
2016, 8, 2210-2213.
[5]. a) T. Fujihara, Y. Tani, K. Semba, J. Terao, Y. Tsuji, Angew. Chem. Int.
Ed. 2012, 51, 11487-11490; b) L. Zhang, J. H. Cheng, B. Carry, Z. M. Hou,
J. Am. Chem. Soc. 2012, 134, 14314-14317; c) T. Fujihara, Y. Horimoto,
T. Mizoe, F. B. Sayyed, Y. Tani, J. Terao, S. Sakaki, Y. Tsuji, Org. Lett.
2014, 16, 4960-4963; d) X. Q. Wang, Y. Liu, R. Martin, J. Am. Chem. Soc.
2015, 137, 6476-6479; e) B. Yu, B. B. Cheng, W. Q. Liu, W. Li, S. S. Wang,
J. Cao, C. W. Hu, Adv. Synth. Catal. 2016, 358, 90-97; f) S. Sun, B. B.
Wang, N. Gu, J. T. Yu, J. Cheng, Org. Lett. 2017, 19, 1088-1091.
[6]. a) M. Takimoto, K. Shimizu, M. Mori, Org. Lett. 2001, 3, 3345-3347; b) K.
Nogi, T. Fujihara, J. Terao, Y. Tsuji, J. Am. Chem. Soc. 2016, 138, 5547-
5550.
[7]. a) M. Takimoto, Z. M. Hou, Chem. Eur. J. 2013, 19, 11439-11445; b) M.
Takimoto, S. S. Gholap, Z. M. Hou, Chem. Eur. J. 2015, 21, 15218-15223;
c) S. Wang, P. Shao, C. Chen, C. J. Xi, Org. Lett. 2015, 17, 5112-5115.
[8]. J. G. Duboudin, B. Jousseaume, A. Saux, J. Organomet. Chem. 1978,
162, 209-222.
[9]. a) E. Shirakawa, T. Yamagami, T. Kimura, S. Yamaguchi, T. Hayashi, J.
Am. Chem. Soc. 2005, 127, 17164-17165; b) T. Yamagami, R. Shintani,
E. Shirakawa, T. Hayashi, Org. Lett. 2007, 9, 1045-1048; c) E. Shirakawa,
D. Ikeda, S. Masui, M. Yoshida, T. Hayashi, J. Am. Chem. Soc. 2012, 134,
272-279; d) F. Xue, J. Zhao, T. S. A. Hor, T. Hayashi, J. Am. Chem. Soc.
2015, 137, 3189-3192.
[10]. a) K. Murakami, H. Ohmiya, H. Yorimitsu, K. Oshima, Org. Lett. 2007, 9,
1569-1571; b) N. Kambe, Y. Moriwaki, Y. Fujii, T. Iwasaki, J. Terao, Org.
Lett. 2011, 13, 4656-4659; c) F. Xue, J. Zhao, T. S. A. Hor, Chem.
Commun. 2013, 49, 10121-10123.
[11]. a) S. Bhuvaneswari, M. Jeganmohan, C. H. Cheng, Chem. Commun.
2008, 5013-5015; b) P. S. Lin, M. Jeganmohan, C. H. Cheng, Chem. Eur.
J. 2008, 14, 11296-11299; c) S. Mannathan, M. Jeganmohan, C. H.
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TOC
CO2 must convert: The key
molecule for the present global
warming “CO2” must be utilized
wherever it applies. Herein,
CO2 Fixation
Chen-Hsun Hung, Rajagopal Santhoshkumar,
Yu-Che Chang, and Chien-Hong Cheng*[a]
CO2 is used for
a nickel-
catalyzed carbomagnesiation
of alkynes to produce acrylic
acids.
Page No. – Page No.
Synthesis of Trisubstituted Acrylic Acids via
Nickel-Catalyzed Carbomagnesiation of
Alkynes and Carbon Dioxide Fixation
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