Rhodium-catalyzed regioselective olefination directed by a carboxylic group

Article abstract of DOI:10.1021/jo200509m

The ortho-olefination of benzoic acids can be achieved effectively through rhodium-catalyzed oxidative coupling with alkenes. The carboxylic group is readily removable to allow ortho-olefination/decarboxylation in one pot. α,β-Unsaturated carboxylic acids

Full text of DOI:10.1021/jo200509m

FEATURED ARTICLE
pubs.acs.org/joc
Rhodium-Catalyzed Regioselective Olefination Directed by a
Carboxylic Group
Satoshi Mochida, Koji Hirano, Tetsuya Satoh,* and Masahiro Miura*
Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
S Supporting Information
b
ABSTRACT: The ortho-olefination of benzoic acids can be
achieved effectively through rhodium-catalyzed oxidative cou-
pling with alkenes. The carboxylic group is readily removable to
allow ortho-olefination/decarboxylation in one pot. R,β-Unsa-
turated carboxylic acids such as methacrylic acid also undergo
the olefination at the β-position. Under the rhodium catalysis,
the cine-olefination of heteroarene carboxylic acids such as
thiophene-2-carboxylic acid proceeds smoothly accompanied
by decarboxylation to selectively produce the corresponding
vinylheteroarene derivatives.
’ INTRODUCTION
Scheme 1. Pd/Cu-Catalyzed Ortho-Olefination
Since vinylarene structures can be widely seen in various fine
chemicals,1 the development of methods for their effective cons-
truction has attracted considerable attention in organic synthesis.
The conventional syntheses of such derivatives through transi-
tion-metal-catalyzed cross-coupling and MizorokiꢀHeck reac-
tions or Wittig-type reactions usually need complicated multis-
teps forming halogen- or phosphorus-containing byproducts.
On the other hand, direct olefination reactions on aromatic rings
involving regioselective CꢀH bond cleavage have been developed to
provide more simple synthetic routes for vinylarene derivatives.2 As
early examples, we reported that 2-phenylphenols (Scheme 1, YH =
2-HOC6H4),3 N-(arylsulfonyl)-2-phenylanilines (YH = 2-(ArSO2
NH)C6H4),4 and benzoic acids (YH = CO2H)4 undergo regioselec-
tive olefination at the ortho-position of YH upon treatment with an
alkene such as acrylate ester (R = CO2R0) and an appropriate oxidant
under palladium/copper catalysis. In each case, subsequent nucleo-
philic cyclization takes place to afford the corresponding heterocyclic
product. Later, aromatic amides,5 benzylamines,6 phenylacetic acids,7
1-phenylprazoles,8 and 2-phenylethanols9 have also been shown to
undergo the direct ortho-olefination under palladium or rhodium
catalysis.
Among these examples, the reaction of benzoic acids and
related carboxylic acids is of particular interest because of their
wide availability as building blocks. Furthermore, if the carboxylic
group remains in the olefinated products without undergoing the
subsequent cyclization, it can be readily removed and further
transformed.10 Therefore, the reaction sequence of ortho-olefina-
tion/decarboxylation seems to be applicable to constructing a wide
range of vinylarenes. In the course of our study of the functionaliza-
tion of carboxylic acids,11 it has been revealed that ortho-olefinated
benzoic acids can be obtained upon treatment of the parent acids
with styrenes in place of acrylates under rhodium catalysis.12 Ex-
pectedly, some of the products underwent decarboxylation during
post-treatment in the same pot to produce stilbene derivatives.
Besides a series of substituted benzoic acids, naphthoic acids,
R,β-unsaturated acids, and heteroarene carboxylic acids also
underwent the regioselective olefination. The details of these
findings are described herein.
’ RESULTS AND DISCUSSION
In an initial attempt, benzoic acid (1a) (0.5 mmol) was treated
with styrene (2a) (1.5 mmol) under conditions similar to those em-
ployed for the reaction with acrylates.4b In the presence of [Cp*Rh
Cl2]2 (0.005 mmol) and Cu(OAc)2 H2O (0.025 mmol) in o-xylene
3
(2.5 mL) at 120 °C under air for 10 h, a mixture of mono- and
diolefinated products was formed, which were subsequently methyl-
esterified for quantification to give 3a and 4a, respectively (entry 1 in
Table 1, Cp* = pentamethylcyclopentadienyl). Under conditions
using a stoichiometric amount of Cu(OAc)2 H2O (2 mmol) in
3
DMF under N2, the yield of 4a was improved to 71% (entry 3).
Moreover, the use of AgOAc (2 mmol) as the oxidant significantly
enhanced the reaction efficiency to produce 4a in 96% yield (entry 4).
The reaction was sluggish at 100 °C or in o-xylene (entries 5 and 6).
Under the conditions employed for entry 4 in Table 1,
the couplings of 1a with 4-methyl- (2b), methoxy- (2c), and
Received: March 8, 2011
Published: March 26, 2011
r
2011 American Chemical Society
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|

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FEATURED ARTICLE
Table 1. Reaction of Benzoic Acid (1a) with Styrene (2a)a
Table 2. Reaction of Benzoic Acids 1 with Styrenes 2a
yieldb (%)
entry
1
R1
R2
2
Ar
product, % yieldb
entry
oxidant (mmol)
solvent temp (°C) 3a
4a
lc
2c
3
Cu(OAc)2 H2O (0.025) o-xylene
120
120
120
120
100
120
19 10
20 12
23 71
1
2
1a
1a
1a
1a
1b
1c
1d
1e
1f
H
H
2b
2c
2d
2e
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
4-ButC6H4
4b, 69
4c, 66
4d, 63
4e, 84
4f, 73
4g, 65
4h, 75
4i, 72
4j, 81
4k, 74
4l, 69
4m, 60
4n, 66
4o, 65
3
H
H
4-MeOC6H4
Cu(OAc)2 H2O (0.025) DMF
3
3
H
H
4-ClC6H4
Cu(OAc)2 H2O (2)
DMF
3
4
H
H
2-naphthyl
4
AgOAc (2)
AgOAc (2)
AgOAc (2)
DMF
4
4
96 (87)
5
Me
OMe
Cl
H
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
5
DMF
43
8
6
H
6
o-xylene
14
a Reaction conditions: (1) 1a (0.5 mmol), 2a (1.5 mmol), [Cp*RhCl2]2
(0.005 mmol), solvent (2.5 mL) under N2 for 10 h: (2) with the addition
of MeI (3 mmol) and K2CO3 (1.5 mmol) at rt for 3 h. b GC yield based
on the amount of 1a used. Value in parentheses indicates yield after
purification. c Under air.
7
H
8
Br
H
9
Ph
Ac
CF3
H
H
10c
11c
12
13
14
1g
1h
1i
H
H
OMe
Cl
F
chloro-substituted (2d) styrenes proceeded smoothly to form
the corresponding 2,6-distyrylbenzoates 4bꢀd (Table 2, entries
1ꢀ3). The reaction of 1a with 2-vinylnaphthalene (2e) occurred
in a similar manner to give a diolefinated product 4e in 84% yield
(entry 4). A series of 4-substituted benzoic acids 1bꢀh under-
went the diolefination to form 4fꢀl (entries 5ꢀ11). For the
reactions of electron-deficient benzoic acids such as 1g and 1h,
increased amounts of the Rh catalyst were needed (entries 10 and
11). The diolefination of 3-methoxy- (1i), chloro- (1j), and
fluoro-substituted (1k) benzoic acids also took place to form
4mꢀo (entries 12ꢀ14).
1j
H
1k
H
a Reaction conditions: (1) 1 (0.5 mmol), 2 (1.5 mmol), [Cp*RhCl2]2
(0.005 mmol), AgOAc (2 mmol), DMF (2.5 mL) under N2 at 120 °C for
8ꢀ10 h; (2) with the addition of MeI (3 mmol) and K2CO3 (1.5 mmol)
at rt for 3 h. b Isolated yield. c With [Cp*RhCl2]2 (0.01 mmol).
Table 3. Reaction of Benzoic and Naphthoic Acids 1 with
Styrene (2a)a
As expected, monoolefinated products 3bꢀi were obtained
upon treatment of 2-substituted or 2,4-disubstituted benzoic
acids 1lꢀs with styrene (2a) under standard conditions (Table 3,
entries 1ꢀ8). Exceptionally, the reactions of 1p and 1r were
conducted at 100 °C (entries 5 and 7). At 120 °C, the products
3f and 3h partly underwent decarboxylation. The reaction
of 3-methylbenzoic acid (1t) also gave monoolefinated 3j
exclusively, in contrast to the cases with other 3-substituted
benzoic acids 1iꢀk, which were selectively transformed to
diolefinated products (entries 12ꢀ14, Table 2). Naphthoic
acids 1u and 1v underwent regioselective monoolefination to
afford 2- and 3-styrylnaphthoates 3k and 3l, respectively (entries
10 and 11).
A plausible mechanism for the ortho-olefination of 1 with 2 is
illustrated in Scheme 2, in which neutral ligands are omitted.
Coordination of the carboxylate oxygen of 1 to Cp*Rh(III)X2
gives a rhodium(III) benzoate A. Subsequent ortho-rhodation to
form a rhodacycle intermediate B,13 styrene insertion, and β-
hydrogen elimination occur to produce a monoolefinated pro-
duct. After the release of the product, the resulting Cp*Rh(I)
species may be oxidized in the presence of a silver(I) or copper-
(II) salt to regenerate Cp*Rh(III)X2. In the cases shown in
Tables 1 and 2, the second olefination may proceed by the same
mechanism.
entry
1
R1
R2
R3
product, % yieldb
1
2
1l
H
H
Me
OMe
Cl
3b, 75
3c, 62
3d, 58
3e, 79
3f, 73
3g, 82
3h, 85
3i, 78
3j, 62
3k, 63
3l, 57
1m
1n
1o
1p
1q
1r
H
H
3
H
H
4
5c
Me
H
Me
OMe
Me
F
OMe
H
6
Cl
H
7c
8
H
H
1s
H
H
Ph
9
1t
H
Me
H
10
11
1u
1v
H
ꢀ(CH)4ꢀ
ꢀ(CH)4ꢀ
H
a Reaction conditions: (1) 1 (0.5 mmol), 2a (1 mmol), [Cp*RhCl2]2
(0.005 mmol), AgOAc (1 mmol), DMF (2.5 mL) under N2 at 120 °C for
8 h; (2) with the addition of MeI (3 mmol) and K2CO3 (1.5 mmol) at rt
for 3 h. b Isolated yield. c At 100 °C.
For providing further mechanistic information, competitive
reactions of d0-benzoic acid (1a-d0) and d5-benzoic acid (1a-d5)
with 2a were conducted under standard olefination conditions
(Scheme 3). In the early stage of these reactions, significant
primary isotopic effects of 2.7 and 9.0 were observed for the
mono- and diolefinated products, respectively, which suggests
that the rate-determining step involves CꢀH(D) bond cleavage
(from A to B in Scheme 2). It was confirmed that H incorpora-
tion was significantly slow (<10%) at the ortho-position(s) of
starting 1a-d5 as well as 3a-dn.
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FEATURED ARTICLE
Scheme 2. Plausible Mechanism for the Reaction of 1 with 2
Table 4. Decarboxylative Olefination of Benzoic and
Naphthoic Acids 1 with Styrenes 2a
entry
1
R1
R2
R3
2
Ar
product, % yieldb
1
2
3
4
5
6
7
8
9
1p OMe
1p OMe
1p OMe
1p OMe
H
H
H
H
H
H
H
H
OMe
OMe
OMe
OMe
OMe
2a Ph
5a, 80
5b, 67
5c, 73
5d, 65
5e, 66
5f, 66
5g, 66
5h, 54
5i, 70
2b 4-ButC6H4
2c 4-MeOC6H4
2d 4-ClC6H4
2a Ph
1m
1w
1r
H
H
H
H
H
NHAc 2a Ph
Scheme 3. Competitive Reaction of 1a-d0 and 1a-d5
F
2a Ph
2a Ph
1s
Ph
1u
ꢀ(CH)4ꢀ 2a Ph
a Reaction conditions: (1) 1 (0.5 mmol), 2 (1 mmol), [Cp*RhCl2]2
(0.005 mmol), AgOAc (1ꢀ1.5 mmol), DMAc (2.5 mL) under N2 at 120
°C for 8 h; (2) with the addition of AgOAc (1 mmol) and K2CO3 (1
mmol) at 160 °C for 4 h. b Isolated yield.
Scheme 4. Decarboxylative Olefination of Benzoic Acids 1
with Styrene (2a)
It was confirmed that the carboxylic group in 2-styrylbenzoic
acids, produced in the monoolefination of 2-substituted benzoic
acids 1m,p,r,s,w and 1-naphthoic acid (1u), can be readily
removed. Thus, after the olefination of 1p (0.5 mmol) as in
Table 3, AgOAc (1 mmol) and K2CO3 (1 mmol) were added
into the same pot and the resulting mixture was heated at 160 °C
for 4 h for decarboxylation.14ꢀ16 As a result, an ortho-olefination/
decarboxylation product, 3,5-dimethoxystilbene (5a) was ob-
tained in 80% yield (Table 4, entry 1). Substituted styrenes 2bꢀd
also reacted with 1p to give substituted stilbenes 5bꢀd (entries
2ꢀ4). It should be noted that the obtained 3,5,40-trimethoxys-
tilbene (5c), an analogue of naturally occurring resveratrol,17 is of
particular interest for its biological activities including anticancer
properties.18 Under similar conditions, 1m,r,s,w also underwent
the decarboxylative olefination to afford the corresponding
3-substituted stilbenes 5eꢀh (entries 5ꢀ8).19 From 1u, 2-styr-
ylnaphthalene (5i) could be synthesized effectively (entry 9).
Unsubstituted benzoic acid (1a) also underwent the decar-
boxylative olefination upon treatment with 2a. In this case,
diolefination at the 2- and 6-positions and subsequent decarbox-
ylation took place to form 1,3-distyrylbenzene (6a)20 selectively
(Scheme 4). The reaction of 4-methoxybenzoic acid (1c) with 2a
also proceeded in a similar manner to give distyrylbenzene 6b.
The olefination of commercially available aromatic dicar-
boxylic acids were next examined. Treatment of isophthalic acid
(7) with 2a under standard olefination conditions and sub-
sequent methyl esterification gave the corresponding monoolefinated
product 8 (Scheme 5). Similar treatment of diphenic acid (9)
afforded a mixture of mono- (10) and diolefinated products (11).
Interestingly, a 1,4-distyrylbenzene derivative, which is of im-
portance in organic material field,21 could be obtained through
the diolefination/decarboxylation of phthalic acid (12) with
2a. In this case, a better result was obtained by using Cu-
(OAc)2 H2O as an oxidant under mild conditions (100 °C).
3
Under the present Rh-catalysis, the regioselective olefination
was found to take place not only on an aromatic but also vinylic
sp2-carbon at the neighboring site of a carboxylic group.11e Thus,
treatment of methacrylic acid (14a) with 2a in the presence of
[Cp*RhCl2]2 (0.005 mmol) and AgOAc (1 mmol) in DMF
(2.5 mL) at 120 °C under N2 for 10 h followed by methyl
esterification gave (2Z,4E)-methyl 2-methyl-5-phenylpenta-2,4-
dienoate (15a) as a regio- and stereoselective olefination product
in 38% yield (Table 5, entry 1). The reaction efficiency was
slightly improved by the use of Cu(OAc)2 H2O as an oxidant
3
(entry 2). With [Cp*RhCl2]2 (0.01 mmol), the product yield
increased to 60% (entry 3). The yield decreased at 100 or 140 °C
(entries 4 and 5). Similarly, 14a and tiglic acid (14b) reacted with
2-vinylnaphthalene (2e) to form the corresponding β-olefinated
products 15b and 15c, respectively (entries 6 and 7).
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FEATURED ARTICLE
Scheme 5. Reaction of Aromatic Dicarboxylic Acids with 2a
Table 6. Reaction of Heteroarene Carboxylic Acids 16 with
Alkenes 2a
Table 5. Reaction of r,β-Unsaturated Carboxylic Acids 14
with Styrenes 2a
a Reaction conditions: 16 (0.5 mmol), [Cp*RhCl2]2 (0.01 mmol),
entry
14
R
2
Ar
temp (°C) product, % yieldb
Cu(OAc)2 H2O (1 mmol), DMF (2.5 mL) under N2 at 140 °C
3
for 6ꢀ8 h. b GC yield based on the amount of 16 used. Value in
parentheses indicates yield after purification. c At 120 °C. d With
1c,d
2c
3
14a
14a
14a
14a
14a
14a
H
2a Ph
2a Ph
2a Ph
2a Ph
2a Ph
120
120
120
100
140
120
120
15a, 38
H
H
H
H
H
15a, 48
AgOAc (1 mmol) in place of Cu(OAc)2 H2O. e With [Cp*RhCl2]2
3
15a, 60 (58)
15a, 50
(0.005 mmol).
4
5
15a, 24
6
2e 2-naphthyl
15b, 70 (64)
3-styrylthiophene (17a) was formed through 3-olefination/dec-
arboxylation even under mild conditions at 120 °C (Table 6,
entry 1). A significant amount of normal 3-olefinated product
possessing the carboxylic group intact was also detected by GC
and GCꢀMS (ca. 20%) after methyl esterification. Increasing
the amount of 2a slightly improved the yield of 17a (entry 2).
At 140 °C, the reaction efficiency was significantly enhanced
to selectively produce 17a in 64% yield (entry 3). AgOAc was
7
14b Me 2e 2-naphthyl
15c, 43 (40)
a Reaction conditions: (1) 14 (0.5 mmol), 2 (1 mmol), [Cp*RhCl2]2
(0.01 mmol), Cu(OAc)2 H2O (1 mmol), DMF (2.5 mL) under N2 for
3
10 h; (2) with the addition of MeI (3 mmol) and K2CO3 (1.5 mmol) at
rt for 3 h. b GC yield based on the amount of 14 used. Value in
parentheses indicates yield after purification. c With [Cp*RhCl2]2 (0.005
mmol). d AgOAc (1 mmol) was used in place of Cu(OAc)2 H2O.
3
less effective as an oxidant than Cu(OAc)2 H2O (entry 4).
Finally, 17 was obtained in 70% yield by using 4 mmol of 2a
(entry 5).
Previously, we have reported that indole-, pyrrole-, and
benzofuran-2-carboxylic acids undergo the carboxylic group
directed 3-olefination/decarboxylation upon treatment with
alkenes and an oxidant under palladium catalysis to produce
3
In general, electron-rich, five-membered heteroarene car-
boxylic acids tend to undergo decarboxylation more readily than
benzoic acids in the presence of an appropriate transition-metal
catalyst.11d,f,g,i,j When thiophene-2-carboxylic acid (16a) (0.5
mmol) was treated with 2a (1 mmol) in the presence of
[Cp*RhCl2]2 (0.01 mmol) and Cu(OAc)2 H2O (1 mmol),
3
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FEATURED ARTICLE
2-vinylheteroarenes.11j However, the application of the palla-
dium-based catalyst system to the reaction of thiophene and
benzothiophene-2-carboxylic acids was problematic, in which
mixtures of 2- and 3-olefinated products were formed. These
acids underwent decarboxylation more reaily under the Pd-
catalyzed conditions. Therefore, at least parts of the 2-olefinated
products seem to arise from the sequence of the initial decarbox-
ylation and subsequent nondirected olefination of the resulting
thiophene and benzothiophene. Under the present rhodium
catalysis, the carboxylic groups may be kept until completion
of the olefination to avoid the 2-olefination.
The Rh-catalyst system could be applied to the reaction of
various heteroarene carboxylic acids 16aꢀe with butyl acrylate
(2f) (entries 6ꢀ10). The reaction proceeded smoothly even
with a reduced amount of rhodium catalyst (1 mol %). In all
cases, the product yields became higher than those in the Pd-
catalyzed reactions, and formation of regioisomers could not be
detected.
added, and the resulting mixture was stirred under air at room temperature
for 3 h. The reaction mixture was then extracted with ethyl acetate
(100 mL). The organic layer was washed with water (100 mL, three
times) and dried over Na2SO4. After evaporation of the solvent under
vacuum, the product was isolated by column chromatography on silica
gel using hexaneꢀethyl acetate (95:5, v/v) as eluant. 3a (20 mg, 17%):
1H NMR (400 MHz, CDCl3) δ 3.93 (s, 3H), 7.01 (d, J = 16.5 Hz, 1H),
7.25ꢀ7.37 (m, 3.7H), 7.49ꢀ7.56 (m, 2.7H), 7.72 (d, J = 7.7 Hz, 0.73H),
7.92ꢀ7.94 (m, 0.76H), 7.99 (d, J = 16.5 Hz, 1H). Kinetic isotope effect
determined by 1H NMR: kH/kD = 0.73/0.27 = 2.7. 4a (9.5 mg, 6%): 1H
NMR (400 MHz, CDCl3) δ 3.98 (s, 3H), 7.06 (d, J = 16.1 Hz, 2H), 7.13
(d, J = 16.1 Hz, 2H), 7.25ꢀ7.30 (m, 2H), 7.34ꢀ7.38 (m, 4H), 0.7.42
(t, J = 7.7 Hz, 0.90H), 7.47ꢀ7.50 (m, 4H), 7.61 (d, J = 7.7 Hz, 1.8H).
Kinetic isotope effect determined by 1H NMR: kH/kD = 0.90/0.10=9.0.
General Procedure for Monoolefination/Decarboxylation
of 2-Subtituted Benzoic Acids with Styrenes. To a 20 mL two-
necked flask with a reflux condenser, a balloon, and a rubber cup were
added 2-substituted benzoic acid 1 (0.5 mmol), styrene 2 (1 mmol),
[(Cp*RhCl2)2] (0.005 mmol, 3 mg), AgOAc (1ꢀ1.5 mmol), 1-methyl-
naphthalene (ca. 50 mg) as internal standard, and DMAc (2.5 mL).
Then, the resulting mixture was stirred under nitrogen at 120 °C for 8 h.
After cooling, AgOAc (1 mmol, 166 mg) and K2CO3 (1 mmol, 138 mg)
were added and the resulting mixture was stirred under nitrogen at
160 °C for 4 h. GC and GCꢀMS analyses of the mixtures confirmed
formation of 5. The reaction mixture was then extracted with ethyl
acetate (100 mL). The organic layer was washed with water (100 mL,
three times) and dried over Na2SO4. After evaporation of the solvent
under vacuum, product 5 was isolated by column chromatography on
silica gel using hexaneꢀethyl acetate (95:5, v/v) as eluant.
’ CONCLUSIONS
In summary, we have demonstrated that the regioselective
olefination of benzoic and naphthoic acids, R,β-unsaturated
carboxylic acids, and heteroarene carboxylic acids with alkenes
can be performed at the neighboring position(s) of their
carboxylic group in the presence of a rhodium catalyst and a
silver or copper salt oxidant. In most cases, the directing group
can be readily removed during the olefination reaction or post-
treatment.
Procedure for Diolefination/decarboxylation of Phthalic
Acid with Styrene. To a 20 mL two-necked flask with a reflux
condenser, a balloon, and a rubber cup were added phthalic acid (12) (0.5
mmol, 83 mg), styrene (2a) (1.5 mmol, 156 mg), [(Cp*RhCl2)2] (0.01
’ EXPERIMENTAL SECTION
General Methods. 1H and 13C NMR spectra were recorded at 400
and 100 MHz for CDCl3 or DMSO-d6 solutions. MS data were obtained
by EI. GC analysis was carried out using a silicon OV-17 column (i.d. 2.6
mm ꢁ 1.5 m). GCꢀMS analysis was carried out using a CBP-1 capillary
column (i.d. 0.25 mm ꢁ 25 m). The structures of all products listed
below were unambiguously determined by 1H and 13C NMR with the
aid of NOE, COSY, HMQC, and HMBC experiments.
All starting materials and reagents were commercially available.
General Procedure for Diolefination of Benzoic Acids with
Styrenes. To a 20 mL two-necked flask with a reflux condenser, a
balloon, and a rubber cup were added benzoic acid 1 (0.5 mmol), styrene
2 (1.5 mmol), [(Cp*RhCl2)2] (0.005 mmol, 3 mg), AgOAc (2 mmol,
333 mg), 1-methylnaphthalene (ca. 50 mg) as internal standard, and
DMF (2.5 mL). The resulting mixture was stirred under nitrogen at
120 °C for 8ꢀ10 h. After the mixture was cooled, iodomethane (3 mmol,
423 mg) and K2CO3 (1.5 mmol, 207 mg) were added, and the resulting
mixture was stirred under air at room temperature for 3 h. GC and GCꢀMS
analyses of the mixtures confirmed formation of 4. The reaction mixture
was then extracted with ethyl acetate (100 mL). The organic layer was
washed with water (100 mL, three times) and dried over Na2SO4. After
evaporation of the solvent under vacuum, product 4 was isolated by
column chromatography on silica gel using hexaneꢀethyl acetate (95:5,
v/v) as eluant.
mmol, 6 mg), Cu(OAc)2 H2O (2 mmol, 400 mg), 1-methylnaphthalene
3
(ca. 50 mg) as internal standard, and DMF (2.5 mL). Then, the resulting
mixture was stirred under nitrogen at 100 °C for 10 h. After cooling,
iodomethane (3 mmol, 423 mg) and K2CO3 (1.5 mmol, 207 mg) were
added, and the resulting mixture was stirred under air at room temperature
for 3 h. GC and GCꢀMS analyses of the mixtures confirmed formation of
13 (104 mg, 61%). Then, the reaction mixture was extracted with ethyl
acetate (100 mL). The organic layer was washed with water (100 mL, three
times) and dried over Na2SO4. After evaporation of the solvent under
vacuum, product 13 (75 mg, 44%) was isolated by column chromatography
on silica gel using hexaneꢀethyl acetate (95:5, v/v) as eluant.
General Procedure for Monoolefination/decarboxylation
of Heteroarene-2-carboxylic Acids with Butyl Acrylate. To a
20 mL two-necked flask with a reflux condenser, a balloon, and a rubber cup
were added heteroarene-2-carboxylic acid 16 (0.5 mmol), butyl acrylate 2f
(1 mmol, 128 mg), [(Cp*RhCl2)2] (0.005 mmol, 3 mg), Cu(OAc)2 H2O
3
(1 mmol, 200 mg), 1-methylnaphthalene (ca. 50 mg) as internal standard,
and DMF (2.5 mL). Then, the resulting mixture was stirred under nitrogen
at 140 °C for 6 h. GC and GCꢀMS analyses of the mixtures confirmed
formation of 19. Then, the reaction mixture was extracted with ethyl acetate
(100 mL). The organic layer was washed with water (100 mL, three times)
and dried over Na2SO4. After evaporation of the solvent under vacuum,
product 19 was isolated by column chromatography on silica gel using
hexaneꢀethyl acetate (85:15, v/v) as eluant.
Procedure for Competitive Reaction of 1a-d0 and 1a-d5.
To a 20 mL two-necked flask with a reflux condenser, a balloon, and a
rubber cup were added d0-benzoic acid (1a-d0) (0.25 mmol, 31 mg), d5-
benzoic acid (1a-d5) (0.25 mmol, 32 mg), styrene (2a) (1.5 mmol,
156 mg), AgOAc (2 mmol, 333 mg), 1-methylnaphthalne (ca. 50 mg) as
internal standard, and DMF (2.5 mL). The resulting mixture was stirred
under N2 at 120 °C for 5 min (Scheme 3). After the mixture was cooled,
iodomethane (3 mmol, 423 mg) and K2CO3 (1.5 mmol, 207 mg) were
(E)-Methyl 2-styrylbenzoate (3a):22. oil; 1H NMR (400 MHz,
CDCl3) δ 3.92 (s, 3H), 6.91 (d, J = 16.5 Hz, 1H), 7.24ꢀ7.38 (m, 4H),
7.49ꢀ7.56 (m, 3H), 7.71 (d, J = 7.7 Hz, 1H), 7.92 (d, J = 7.7 Hz, 1H),
7.99 (d, J = 16.5 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 52.1,
126.8, 127.0, 127.1, 127.4, 127.8, 128.5, 128.6, 130.7, 131.4, 132.1, 137.4,
139.2, 167.9; HRMS m/z calcd for C16H14O2 (Mþ) 238.0994, found
238.0992.
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FEATURED ARTICLE
(E)-Methyl 2-methyl-6-styrylbenzoate (3b): oil; 1H NMR
(400 MHz, CDCl3) δ 2.23 (s, 3H), 3.83 (s, 3H), 6.93 (d, J = 16.0 Hz,
1H), 6.99ꢀ7.05 (m, 2H), 7.13ꢀ7.18 (m, 2H), 7.19ꢀ7.25 (m, 2H), 7.36
(d, J = 7.4 Hz, 2H), 7.40 (d, J = 7.8 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 19.6, 52.0, 123.0, 125.6, 126.6, 127.9, 128.6, 129.2, 129.5,
131.3, 132.8, 134.9, 135.2, 137.0, 170.1; HRMS m/z calcd for C17H16O2
(Mþ) 252.1150, found 252.1150.
(m, 2H), 7.33ꢀ7.37 (m, 2H), 7.44ꢀ7.52 (m, 4H), 7.77ꢀ7.83 (m, 4H);
13C NMR (100 MHz, CDCl3) δ 52.4, 122.6, 125.0, 125.4, 126.2, 126.7,
127.3, 128.0, 128.1, 128.7, 129.8, 129.9, 130.0, 131.9, 132.4, 132.5, 136.9,
169.9; HRMS m/z calcd for C20H16O2 (Mþ) 288.1150, found
288.1148.
(E)-Methyl 3-styryl-2-naphthoate (3l): oil; 1H NMR (400
MHz, CDCl3) δ 3.96 (s, 3H), 7.06 (d, J = 16.0 Hz, 1H), 7.23ꢀ7.28
(m, 1H), 7.35ꢀ7.38 (m, 2H), 7.45ꢀ7.59 (m, 4H), 7.84ꢀ7.87 (m, 2H),
8.03 (d, J = 16.0 Hz, 1H), 8.08 (s, 1H), 8.48 (s, 1H); 13C NMR (100
MHz, CDCl3) δ 52.2, 126.0, 126.5, 126.8, 126.9, 127.7 (overlapped),
127.9, 128.4, 128.6, 128.7, 130.9, 131.6, 132.0, 134.9, 135.5, 137.6, 167.8;
HRMS m/z calcd for C20H16O2 (Mþ) 288.1150, found 288.1144.
(E,E)-Methyl 2,6-distyrylbenzoate (4a):12. mp 116ꢀ118 °C;
1H NMR (400 MHz, CDCl3) δ 3.96 (s, 3H) 7.05 (d, J = 16.1 Hz, 2H),
7.13 (d, J = 16.1 Hz, 2H), 7.26ꢀ7.28 (m, 2H), 7.33ꢀ7.41 (m, 5H), 7.47
(d, J = 8.0 Hz, 4H), 7.58 (d, J = 8.0 Hz, 2H); 13C NMR (100 MHz,
CDCl3) δ 52.3, 124.6, 125.3, 126.7, 128.0, 128.7, 129.7, 131.8, 131.9,
135.3, 136.9, 169.9; MS m/z 340. Anal. Calcd for C24H20O2: C, 84.68;
H, 5.92. Found: C, 84.46; H, 5.77.
1
(E)-Methyl 2-methoxy-6-styrylbenzoate (3c): oil; H NMR
(400 MHz, CDCl3) δ 3.83 (s, 3H), 3.95 (s, 3H), 6.83 (d, J = 7.8 Hz, 1H),
7.03 (d, J = 16.0 Hz, 1H), 7.09 (d, J = 16.0 Hz, 1H), 7.24ꢀ7.29 (m, 2H),
7.32ꢀ7.36 (m, 3H), 7.46 (d, J = 8.3 Hz, 2H); 13C NMR (100 MHz,
CDCl3) δ 52.4, 55.9, 109.8, 117.6, 122.7, 124.8, 126.7, 128.0, 128.6,
130.5, 131.8, 136.1, 136.9, 156.5, 168.6; HRMS m/z calcd for C17H16O3
(Mþ) 268.1099, found 268.1096.
(E)-Methyl 2-chloro-6-styrylbenzoate (3d): oil; 1H NMR
(400 MHz, CDCl3) δ 3.98 (s, 3H), 7.01 (d, J = 16.5 Hz, 1H), 7.08
(d, J = 16.5 Hz, 1H), 7.24ꢀ7.37 (m, 5H), 7.46 (d, J = 7.8 Hz, 2H), 7.57
(d, J = 7.4 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 52.7, 123.7, 124.1,
126.8, 128.1, 128.4, 128.7, 130.4, 131.1, 132.5, 132.8, 136.4, 136.7, 167.6;
HRMS m/z calcd for C16H13ClO2 (Mþ) 272.0604, found 272.0610.
(E)-Methyl 2,4-dimethyl-6-styrylbenzoate (3e): oil; 1H NMR
(400 MHz, CDCl3) δ 2.31 (s, 3H), 2.34 (s, 3H), 3.92 (s, 3H), 6.93 (s,
1H), 7.02 (d, J = 16.0 Hz, 1H), 7.14 (d, J = 16.0 Hz, 1H), 7.23ꢀ7.27 (m,
1H), 7.32ꢀ7.36 (m, 3H), 7.46 (d, J = 6.9 Hz, 2H); 13C NMR (100 MHz,
CDCl3) δ 19.7, 21.2, 52.0, 123.6, 125.8, 126.6, 127.8, 128.6, 130.1, 130.2,
130.9, 135.0, 135.3, 137.1, 139.4, 170.3; HRMS m/z calcd for C18H18O2
(Mþ) 266.1307, found 266.1308.
(E,E)-Methyl 2,6-bis(4-tert-butylstyryl)benzoate (4b): mp
1
120ꢀ122 °C; H NMR (400 MHz, CDCl3) δ 1.32ꢀ1.33 (m, 18H),
3.95 (s, 3H), 7.04 (d, J = 16.0 Hz, 2H), 7.10 (d, J = 16.0 Hz, 2H),
7.36ꢀ7.43 (m, 9H), 7.56 (d, J = 7.8 Hz, 2H); 13C NMR (100 MHz,
CDCl3) δ 31.2, 34.6, 52.3, 124.3, 124.5, 125.6, 126.5, 129.7, 131.5, 131.7,
134.2, 135.4, 151.2, 170.0; MS m/z 452. Anal. Calcd for C32H36O2: C,
84.91; H, 8.02. Found: C, 84.70; H, 8.00.
(E,E)-Methyl 2,6-bis(4-methoxystyryl)benzoate (4c): mp
12
1
1
(E)-Methyl 2,4-dimethoxy-6-styrylbenzoate (3f): . oil; H
NMR (400 MHz, CDCl3) δ 3.80 (s, 3H), 3.85 (s, 3H), 3.91 (s, 3H), 6.40
(s, 1H), 6.76 (s, 1H), 7.04 (d, J = 16.0 Hz, 1H), 7.10 (d, J = 16.0 Hz, 1H),
7.26 (t, J = 7.3 Hz, 1H), 7.34 (t, J = 7.3 Hz, 2H), 7.46 (d, J = 7.3 Hz, 2H);
13C NMR (100 MHz, CDCl3) δ 55.2, 55.4, 55.9, 97.9, 101.4, 115.8,
125.3, 126.7, 128.0, 128.6, 131.6, 136.7, 137.4, 158.1, 161.4, 168.4;
HRMS m/z calcd for C18H18O4 (Mþ) 298.1205, found 298.1209.
(E)-Methyl 4-chloro-2-methyl-6-styrylbenzoate (3g): oil;
1H NMR (400 MHz, CDCl3) δ 2.30 (s, 3H), 3.92 (s, 3H), 6.98ꢀ7.07
(m, 2H), 7.09 (s, 1H), 7.25ꢀ7.29 (m, 1H), 7.34 (t, J = 7.8 Hz, 2H), 7.45
(d, J = 7.8 Hz, 2H), 7.48 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 19.6,
52.2, 122.9, 124.3, 126.8, 128.2, 128.7, 128.9, 131.2, 132.5, 135.4, 136.5,
136.9, 137.4, 169.3; HRMS m/z calcd for C17H15ClO2 (Mþ) 286.0761,
found 286.0757.
156ꢀ157 °C; H NMR (400 MHz, CDCl3) δ 3.80 (s, 6H), 3.96 (s,
3H), 6.88 (d, J = 8.7 Hz, 4H), 6.96 (d, J = 16.0 Hz, 2H), 7.02 (d, J = 16.0
Hz, 2H), 7.34ꢀ7.42 (m, 5H), 7.53 (d, J = 8.7 Hz, 2H); 13C NMR (100
MHz, CDCl3) δ 52.3, 55.2, 114.1, 123.1, 124.0, 127.9, 129.6, 129.8,
131.1, 131.4, 135.5, 159.5, 170.1; HRMS m/z calcd for C26H24O4 (Mþ)
400.1675, found 400.1673.
(E,E)-Methyl 2,6-bis(4-chlorostyryl)benzoate (4d): mp 178ꢀ
180 °C; 1H NMR (400 MHz, CDCl3) δ 3.80 (s, 3H), 7.00 (d, J = 16.0 Hz,
2H), 7.09 (d, J = 16.0 Hz, 2H), 7.32 (d, J = 7.8 Hz, 4H), 7.38ꢀ
7.43 (m, 5H), 7.58 (d, J = 7.8 Hz, 2H); 13C NMR (100 MHz, CDCl3)
δ 52.5, 124.9, 125.8, 127.9, 128.9, 129.9, 130.6, 131.9, 133.7, 135.2, 135.4,
169.8; HRMS m/z calcd for C24H18Cl2O2 (Mþ) 408.0684, found
408.0681.
Methyl 2,6-bis((E)-2-(naphthalen-2-yl)vinyl)benzoate (4e):
mp 207ꢀ208 °C; 1H NMR (400 MHz, CDCl3) δ 4.03 (s, 3H) 7.23 (d,
J = 16.0 Hz, 2H), 7.28 (d, J = 16.0 Hz, 2H), 7.43ꢀ7.50 (m, 5H),
7.65ꢀ7.71 (m, 4H), 7.80ꢀ7.84 (m, 8H); 13C NMR (100 MHz, CDCl3)
δ 52.5, 123.5, 124.7, 125.6, 126.1, 126.4, 127.2, 127.7, 128.1, 128.4,
129.9, 131.91, 131.93, 133.2, 133.6, 134.4, 135.5, 170.0; HRMS m/z
calcd for C32H24O2 (Mþ) 440.1776, found 440.1775.
(E,E)-Methyl 4-methyl-2,6-distyrylbenzoate (4f): mp 142ꢀ
143 °C; 1H NMR (400 MHz, CDCl3) δ 2.40 (s, 3H), 3.95 (s, 3H), 7.03
(d, J = 16.5 Hz, 2H), 7.14 (d, J = 16.5 Hz, 2H), 7.24ꢀ7.27 (m, 2H), 7.34
(t, J = 7.8 Hz, 4H), 7.40 (s, 2H), 7.47 (d, J = 7.8 Hz, 4H); 13C NMR (100
MHz, CDCl3) δ 21.5, 52.2, 125.4, 125.5, 126.7, 127.9, 128.6, 129.3,
131.4, 135.4, 137.0, 139.6, 170.0; HRMS m/z calcd for C25H22O2 (Mþ)
354.1620, found 354. 1622.
(E)-Methyl 2-fluoro-6-styrylbenzoate (3h): oil; 1H NMR (400
MHz, CDCl3) δ 3.87 (s, 3H), 6.91 (t, J = 8.7 Hz, 1H), 6.98 (d, J = 16.5 Hz,
1H), 7.15ꢀ7.21 (m, 2H), 7.25ꢀ7.28 (m, 3H), 7.37ꢀ7.40 (m, 3H); 13C
NMR (100 MHz, CDCl3) δ52.6, 114.5 (d, J= 22 Hz), 120.3 (d, J=17Hz),
121.3 (d, J = 2.9 Hz), 124.4 (d, J = 2.9 Hz), 126.8, 128.3, 128.7, 131.4 (d, J =
8.6 Hz), 132.7, 136.6, 138.2 (d, J = 2.9 Hz), 160.1 (d, J = 250 Hz), 165.9;
HRMS m/z calcd for C16H13FO2 (Mþ) 256.0900, found 256.0902.
(E)-Methyl 3-styrylbiphenyl-2-carboxylate (3i): mp 106ꢀ
1
107 °C; H NMR (400 MHz, CDCl3) δ 3.57 (s, 3H), 7.10 (d, J =
16.1 Hz, 1H), 7.23ꢀ7.28 (m, 3H), 7.32ꢀ7.39 (m, 7H), 7.43 (t, J = 7.7
Hz, 1H), 7.48 (d, J = 7.3 Hz, 2H), 7.68 (d, J = 7.7 Hz, 1H); 13C NMR
(100 MHz, CDCl3) δ 52.0, 124.3, 125.2, 126.7, 127.4, 128.0, 128.1,
128.3, 128.6, 128.8, 129.6, 132.0, 132.2, 135.3, 136.9, 140.5, 140.6, 169.8;
HRMS m/z calcd for C22H18O2 (Mþ) 314.1307, found 314.1305.
(E)-Methyl 5-methyl-2-styrylbenzoate (3j): oil; 1H NMR (400
MHz, CDCl3) δ 2.37 (s, 3H), 3.92 (s, 3H), 6.97 (d, J = 16.5 Hz, 1H),
7.23ꢀ7.36 (m, 4H), 7.54 (d, J = 7.8 Hz, 2H), 7.60ꢀ7.63 (m, 1H), 7.73
(s, 1H), 7.95 (d, J = 16.5 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 21.0,
52.0, 126.7, 126.8, 127.2, 127.6, 128.3, 128.6, 130.5, 131.0, 133.0, 136.3,
137.0, 137.5, 168.0; HRMS m/z calcd for C17H16O2 (Mþ) 252.1150,
found 252.1152.
(E,E)-Methyl 4-methoxy-2,6-distyrylbenzoate (4g): mp
1
142ꢀ143 °C; H NMR (400 MHz, CDCl3) δ 3.77 (s, 3H), 3.83 (s,
3H), 6.91 (d, J = 16.0 Hz, 2H), 6.99 (s, 2H), 7.08 (d, J = 16.0 Hz, 2H),
7.14ꢀ7.18 (m, 2H), 7.22ꢀ7.25 (m, 4H), 7.37 (d, J = 7.3 Hz, 4H); 13C
NMR (100 MHz, CDCl3) δ 52.2, 55.3, 110.2, 124.8, 125.6, 126.7, 128.0,
128.6, 131.7, 136.8, 137.5, 160.4, 169.7; HRMS m/z calcd for C25H22O3
(Mþ) 370.1569, found 370.1558.
(E,E)-Methyl 4-chloro-2,6-distyrylbenzoate (4h): mp 151ꢀ
152 °C; 1H NMR (400 MHz, CDCl3) δ 3.98 (s, 3H), 7.03ꢀ
7.10 (m, 4H), 7.28ꢀ7.32 (m, 2H), 7.35ꢀ7.39 (m, 4H), 7.48
(E)-Methyl 2-styryl-1-naphthoate (3k): oil; 1H NMR (400
MHz, CDCl3) δ 4.06 (s, 3H), 7.20 (d, J = 16.5 Hz, 1H), 7.27ꢀ7.29
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FEATURED ARTICLE
(d, J = 7.4 Hz, 4H), 7.57 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 52.6,
124.1, 124.3, 126.9, 128.4, 128.8, 130.1, 132.9, 136.0, 136.5, 137.3, 169.2;
MS m/z 374, 376. Anal. Calcd for C24H19ClO2: C, 76.90; H, 5.11; Cl,
9.46. Found: C, 76.62; H, 4.94; Cl, 9.28.
(E,E)-Methyl 4-bromo-2,6-distyrylbenzoate (4i): mp 166ꢀ
167 °C; 1H NMR (400 MHz, CDCl3) δ 3.96 (s, 3H), 7.00ꢀ
7.04 (m, 4H), 7.26ꢀ7.30 (m, 2H), 7.33ꢀ7.37 (m, 4H), 7.45 (d, J =
7.3 Hz, 4H), 7.69 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 52.5, 123.9,
124.3, 126.9, 127.2, 128.4, 128.7, 130.5, 132.9, 136.4, 137.4, 169.2; MS
m/z 418, 420. Anal. Calcd for C24H19BrO2: C, 68.75; H, 4.57; Br, 19.06.
Found: C, 68.49; H, 4.42; Br, 19.03.
δ 55.3, 100.0, 104.6, 126.6, 127.7, 128.7 (overlapped), 129.2, 137.1,
139.3, 161.0; HRMS m/z calcd for C16H16O2 (Mþ) 240.1150, found
240.1145.
(E)-40-tert-Butyl-3,5-dimethoxystilbene (5b):12. oil; 1H NMR
(400 MHz, CDCl3) δ 1.32 (s, 9H), 3.80 (s, 6H), 6.37 (t, J = 2.3 Hz, 1H),
6.66 (d, J = 2.3 Hz, 2H), 6.98 (d, J = 16.0 Hz, 1H), 7.06 (d, J = 16.0 Hz,
1H), 7.36 (d, J = 8.7 Hz, 2H), 7.43 (d, J = 8.7 Hz, 2H); 13C NMR (100
MHz, CDCl3) δ 31.2, 34.6, 55.3, 99.8, 104.4, 125.6, 126.3, 127.8, 128.9,
134.3, 139.5, 150.8, 160.9; HRMS m/z calcd for C20H24O2 (Mþ)
296.1776, found 296.1779.
(E)-3,5,40-Trimethoxystilbene (5c):12. mp 52ꢀ54 °C; 1H NMR
(400 MHz, CDCl3) δ 3.805 (s, 3H), 3.810 (s, 6H), 6.37 (t, J = 2.3 Hz,
1H), 6.64 (d, J = 2.3 Hz, 2H), 6.87ꢀ6.91 (m, 3H), 7.03 (d, J = 16.0 Hz,
1H), 7.43 (d, J = 8.7 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 55.2,
55.3, 99.5, 104.3, 114.1, 126.5, 127.8, 128.7, 129.9, 139.6, 159.3, 160.9;
HRMS m/z Calcd for C17H18O3 (Mþ) 270.1256, found 270.1252.
(E)-40-Chloro-3,5-dimethoxystilbene (5d):12. mp 72ꢀ73 °C;
1H NMR (400 MHz, CDCl3) δ 3.80 (s, 6H), 6.39ꢀ6.40 (t, J = 2.2 Hz,
1H), 6.63 (d, J = 2.2 Hz, 2H), 6.95 (d, J = 16.5 Hz, 1H), 7.00 (d, J = 16.5
Hz, 1H), 7.29 (d, J = 8.8 Hz, 2H), 7.39 (d, J = 8.8 Hz, 2H); 13C NMR
(100 MHz, CDCl3) δ 55.3, 100.1, 104.6, 127.7, 127.8, 128.7, 129.2,
133.2, 135.6, 138.9, 160.9; HRMS m/z calcd for C16H15ClO2 (Mþ)
274.0761, found 274.0756.
(E,E)-Methyl 3,5-distyrylbiphenyl-4-carboxylate (4j): mp
1
137ꢀ138 °C; H NMR (400 MHz, CDCl3) δ 3.97 (s, 3H), 7.10 (d,
J = 16.0 Hz, 2H), 7.20 (d, J = 16.0 Hz, 2H), 7.24ꢀ7.28 (m, 2H),
7.32ꢀ7.41 (m, 5H), 7.45ꢀ7.50 (m, 6H), 7.65 (d, J = 7.8 Hz, 2H), 7.76
(s, 2H); 13C NMR (100 MHz, CDCl3) δ 52.4, 123.6, 125.4, 126.7,
127.3, 127.9, 128.1, 128.7, 128.8, 130.6, 132.0, 136.0, 136.9, 140.3, 142.8,
169.8; MS m/z 416. Anal. Calcd for C30H24O2: C, 86.51; H, 5.81.
Found: C, 86.12; H, 5.71.
(E,E)-Methyl 4-acetyl-2,6-distyrylbenzoate (4k): mp 155ꢀ
156 °C; 1H NMR (400 MHz, CDCl3) δ 2.69 (s, 3H), 4.00 (s, 3H), 7.09
(d, J = 16.0 Hz, 2H), 7.16 (d, J = 16.0 Hz, 2H), 7.28ꢀ7.31 (m, 2H),
7.35ꢀ7.39 (m, 4H), 7.49 (d, J = 7.4 Hz, 4H), 8.13 (s, 2H); 13C NMR
(100 MHz, CDCl3) δ 26.8, 52.6, 124.1, 124.3, 126.8, 128.4, 128.7, 132.9,
135.3, 135.9, 136.5, 137.8, 169.2, 197.5; MS m/z 382. Anal. Calcd for
C26H22O3: C, 81.65; H, 5.80 Found: C, 81.55; H, 5.65.
(E,E)-Methyl 2,6-distyryl-4-(trifluoromethyl)benzoate (4l):
mp 186ꢀ187 °C; 1H NMR (400 MHz, CDCl3) δ 4.01 (s, 3H), 7.08 (d,
J = 16.0 Hz, 2H), 7.14 (d, J = 16.0 Hz, 2H), 7.30ꢀ7.33 (m, 2H),
7.36ꢀ7.40 (m, 4H), 7.50 (d, J = 7.3 Hz, 4H), 7.81 (s, 2H); 13C NMR
(100 MHz, CDCl3) δ 52.7, 121.1 (q, J = 3.8 Hz), 123.7 (q, J = 272 Hz),
123.9, 126.9, 128.6, 128.8, 132.0 (q, J = 32 Hz), 133.5, 134.5, 136.4
(overlapped), 169.0; MS m/z 408. Anal. Calcd for C25H19F3O2: C,
73.52; H, 4.69; F, 13.96. Found: C, 73.25; H, 4.51; F, 13.98.
(E,E)-Methyl 3-methoxy-2,6-distyrylbenzoate (4m): mp
95ꢀ96 °C; 1H NMR (400 MHz, CDCl3) δ 3.85 (s, 3H), 3.86 (s, 3H),
6.91ꢀ6.98 (m, 2H), 7.02ꢀ7.09 (m, 2H), 7.17 (d, J = 16.5 Hz, 1H),
7.20ꢀ7.26 (m, 2H), 7.31ꢀ7.35 (m, 4H), 7.44ꢀ7.48 (m, 4H), 7.57 (d,
J = 8.7 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 52.4, 55.7, 111.9, 122.6,
124.2, 124.8, 125.5, 126.49, 126.53, 127.4, 127.6, 127.7, 128.5, 128.6,
129.8, 133.3, 133.7, 137.2, 137.6, 156.9, 170.0; HRMS m/z calcd for
C25H22O3 (Mþ) 370.1569, found 370.1575.
(E)-3-Methoxystilbene (5e):12. oil; 1H NMR (400 MHz, CDCl3)
δ 3.71 (s, 3H), 6.79ꢀ6.81 (m, 1H), 7.03ꢀ7.09 (m, 4H), 7.21ꢀ7.27 (m,
2H), 7.33 (t, J = 7.7 Hz, 2H), 7.48 (d, J = 7.7 Hz, 2H); 13C NMR (100
MHz, CDCl3) δ 55.1, 111.7, 113.2, 119.2, 126.5, 127.6, 128.5, 128.6,
128.9, 129.6, 137.2, 138.7, 159.8; HRMS m/z Calcd for C15H14O (Mþ)
210.1045, found 210.1039.
(E)-N-(3-Styrylphenyl)acetamide (5f):12. mp 188ꢀ190 °C; 1H
NMR (400 MHz, DMSO-d6) δ 2.08 (s, 3H), 7.16 (d, J = 16.5 Hz, 1H),
7.24 (d, J = 16.5 Hz, 1H), 7.27ꢀ7.32 (m, 3H), 7.39 (t, J = 7.8 Hz, 2H),
7.47ꢀ7.50 (m, 1H), 7.63 (d, J = 7.8 Hz, 2H), 7.84 (s, 1H), 10.0 (s, 1H);
13C NMR (100 MHz, DMSO-d6) δ 24.1, 117.1, 118.6, 121.3, 126.6,
127.7, 128.50, 128.52, 128.7, 129.0, 136.9, 137.4, 139.7, 168.4; HRMS
m/z calcd for C16H15NO (Mþ) 237.1154, found 237.1152.
(E)-3-Fluorostilbene (5g):12. mp 70ꢀ71 °C; 1H NMR (400
MHz, CDCl3) δ 6.91ꢀ6.95 (m, 1H), 7.02 (d, J = 16.5 Hz, 1H), 7.08
(d, J = 16.5 Hz, 1H), 7.17ꢀ7.30 (m, 4H), 7.34 (t, J = 7.8 Hz, 2H), 7.48
(d, J = 7.8 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 112.7 (d, J = 21.9
Hz), 114.3 (d, J = 21.0 Hz), 122.4 (d, J = 2.86 Hz), 126.6, 127.4 (d, J =
2.86 Hz), 128.0, 128.7, 129.96, 130.0 (d, J = 8.58 Hz), 136.8, 139.6 (d, J =
7.63 Hz), 163.1 (d, J = 244 Hz); HRMS m/z calcd for C14H11F (Mþ)
198.0845, found 198.0840.
(E,E)-Methyl 3-chloro-2,6-distyrylbenzoate (4n). mp 113ꢀ
1
115 °C; H NMR (400 MHz, CDCl3) δ 3.82 (s, 3H), 6.80 (d, J =
(E)-3-Styrylbiphenyl (5h):12. mp 91ꢀ93 °C; 1H NMR (400
MHz, CDCl3) δ 7.16ꢀ7.20 (m, 2H), 7.24ꢀ7.27 (m, 1H), 7.34ꢀ7.53
(m, 10H), 7.62 (d, J = 7.8 Hz, 2H), 7.71 (s, 1H); 13C NMR (100 MHz,
CDCl3) δ 125.35, 125.40, 126.50, 126.54, 127.2, 127.4, 127.7, 128.6,
128.7, 128.8, 129.0, 129.1, 137.2, 137.8, 141.1, 141.7; HRMS m/z calcd
for C20H16 (Mþ) 256.1252, found 256.1251.
16.5 Hz, 1H), 7.03ꢀ7.12 (m, 2H), 7.22 (d, J = 16.5 Hz, 1H), 7.28ꢀ7.38
(m, 6H), 7.42 (d, J = 8.7 Hz, 1H), 7.46ꢀ7.50 (m, 4H), 7.54 (d, J =
8.7 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 52.6, 124.0, 124.2, 125.2,
126.7, 126.8, 128.2, 128.3, 128.68, 128.71, 130.5, 132.3, 132.9, 133.4,
133.9, 134.3, 135.0, 136.6 (overlapped), 169.2; HRMS m/z calcd for
C24H19ClO2 (Mþ) 374.1074, found 374.1065.
(E)-2-Styrylnaphthalene (5i):12. mp 144ꢀ146 °C; 1H NMR
(400 MHz, CDCl3) δ 7.07ꢀ7.17 (m, 3H), 7.24ꢀ7.37 (m, 4H), 7.44
(d, J = 8.2 Hz, 2H), 7.60 (d, J = 8.2 Hz, 1H), 7.67ꢀ7.71 (m, 4H); 13C
NMR (100 MHz, CDCl3) δ 123.5, 125.9, 126.3, 126.5, 126.6, 127.6,
127.7, 128.0, 128.3, 128.68, 128.71, 129.0, 133.0, 133.7, 134.8, 137.3;
HRMS m/z calcd for C18H14 (Mþ) 230.1096, found 230.1098.
(E,E)-Methyl 3-fluoro-2,6-distyrylbenzoate (4o): mp 82ꢀ
1
83 °C; H NMR (400 MHz, CDCl3) δ 3.93 (s, 3H), 6.94ꢀ7.01 (m,
2H), 7.06 (d, J = 16.0 Hz, 1H), 7.11ꢀ7.19 (m, 2H), 7.25ꢀ7.30 (m, 2H),
7.33ꢀ7.37 (m, 4H), 7.45ꢀ7.48 (m, 4H), 7.52 (m, 1H); 13C NMR (100
MHz, CDCl3) δ 52.6, 117.3 (d. J = 24 Hz), 119.5, 123.1 (d, J = 14 Hz),
124.2, 125.7 (d, J = 8.6 Hz), 126.7 (overlapped), 128.1, 128.3, 128.7
(overlapped), 131.3 (d, J = 3.8 Hz), 131.6 (overlapped), 133.6 (d, J = 3.8
Hz), 135.8 (d, J = 9.5 Hz), 136.9 (d, J = 24 Hz), 159.7 (d, J = 250 Hz),
169.0 (d, J = 2.9 Hz); MS m/z 358. Anal. Calcd for C24H19FO2: C,
80.43; H, 5.34; F, 5.30. Found: C, 80.15; H, 5.27; F, 5.27.
12
1
(E,E)-1,3-Distyrylbenzene (6a): . mp 162ꢀ163 °C; H NMR
(400 MHz, CDCl3) δ 7.04ꢀ7.12 (m, 4H), 7.17ꢀ7.23 (m, 2H),
7.29ꢀ7.37 (m, 7H), 7.47 (d, J = 7.8 Hz, 4H), 7.58 (s, 1H); 13C NMR
(100 MHz, CDCl3) δ 124.7, 125.7, 126.5, 127.7, 128.5, 128.7, 129.0
(overlapped), 137.2, 137.7; HRMS m/z calcd for C22H18 (Mþ)
282.1409, found 282.1404.
12
1
(E)-3,5-Dimethoxystilbene (5a): . mp 53ꢀ55 °C; H NMR
(400 MHz, CDCl3) δ 3.83 (s, 6H), 6.40 (s, 1H), 6.67 (s, 2H), 7.03 (d, J =
16.5 Hz, 1H), 7.08 (d, J = 16.5 Hz, 1H), 7.24ꢀ7.27 (m, 1H), 7.35 (t, J =
7.7 Hz, 2H), 7.50 (d, J = 7.7 Hz, 2H); 13C NMR (100 MHz, CDCl3)
(E,E)-1,3-Distyryl-5-methoxybenzene (6b): mp 128ꢀ129 °C;
1H NMR (400 MHz, CDCl3) δ 3.86 (s, 3H), 6.96 (s, 2H), 7.06
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FEATURED ARTICLE
(d, J = 16.0 Hz, 2H), 7.12 (d, J = 16.0 Hz, 2H), 7.24ꢀ7.28 (m, 3H),
7.34ꢀ7.37 (m, 4H), 7.50 (d, J = 7.4 Hz, 4H); 13C NMR (100 MHz,
CDCl3) δ 55.3, 111.1, 118.0, 126.5, 127.7, 128.4, 128.7, 129.2, 137.1, 138.9,
160.1; HRMS m/z calcd for C23H20O (Mþ) 312.1514, found 312.1510.
(E)-Dimethyl 4-styrylisophthalate (8): oil; 1H NMR (400
MHz, CDCl3) δ 3.94 (s, 3H), 3.95 (s, 3H), 7.11 (d, J = 16.5 Hz, 1H),
7.28ꢀ7.31 (m, 1H), 7.37 (t, J = 7.8 Hz, 2H), 7.56 (d, J = 7.8 Hz, 2H),
7.79 (d, J = 8.2 Hz, 1H), 8.04 (d, J = 16.5 Hz, 1H), 8.13 (d, J = 8.2 Hz,
1H), 8.58 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 52.2, 52.3, 126.2,
126.9, 127.1, 128.36, 128.41, 128.6, 128.7, 132.2, 132.7, 133.6, 136.8,
143.4, 166.1, 167.0; HRMS m/z calcd for C18H16O4 (Mþ) 296.1049,
found 296.1048.
137.3, 140.1; HRMS m/z (Mþ) calcd for C12H10S 186.0503, found
186.0500.
Butyl (E)-3-(thien-3-yl)-2-propenoate (17b):11j. oil; 1H NMR
(400 MHz, CDCl3) δ 0.96 (t, J = 7.3 Hz, 3H), 1.40ꢀ1.46 (m, 2H),
1.64ꢀ1.71 (m, 2H), 4.20 (t, J = 6.4 Hz, 2H), 6.26 (d, J = 16.0 Hz, 1H),
7.28ꢀ7.33 (m, 2H), 7.47ꢀ7.48 (m, 1H), 7.66 (d, J = 16.0 Hz, 1H); 13C
NMR (100 MHz, CDCl3) δ 13.6, 19.1, 30.7, 64.2, 117.9, 125.1, 126.8,
127.9, 137.5, 137.9, 167.2; HRMS m/z (Mþ) calcd for C11H14O2S
210.0715, found 210.0713.
Butyl (E)-3-(benzo[b]thien-3-yl)-2-propenoate (17c):11j
.
oil; 1H NMR (400 MHz, CDCl3) δ 0.98 (t, J = 7.3 Hz, 3H),
1.44ꢀ1.49 (m, 2H), 1.70ꢀ1.74 (m, 2H), 4.25 (t, J = 6.9 Hz, 2H),
6.54 (d, J = 16.0 Hz, 1H), 7.40ꢀ7.48 (m, 2H), 7.74 (s, 1H), 7.87 (d, J =
7.8 Hz, 1H), 7.96 (d, J = 16.0 Hz, 1H), 8.01 (d, J = 7.8 Hz, 1H); 13C
NMR (100 MHz, CDCl3) δ 13.7, 19.2, 30.7, 64.4, 118.7, 122.0, 122.9,
124.9, 125.0, 127.9, 131.6, 136.2, 137.1, 140.4, 167.2; HRMS m/z (Mþ)
calcd for C15H16O2S 260.0871, found 260.0870.
(E)-Dimethyl 3-styrylbiphenyl-2,20-dicarboxylate (10): mp
88ꢀ90 °C; 1H NMR (400 MHz, CDCl3) δ 3.49 (s, 3H), 3.65 (s, 3H),
7.10 (d, J = 16.1 Hz, 1H), 7.17 (d, J = 7.7 Hz, 1H), 7.22ꢀ7.29 (m, 3H),
7.35 (t, J = 7.3 Hz, 2H), 7.40ꢀ7.54 (m, 5H), 7.71 (d, J = 7.7 Hz, 1H),
7.97 (d, J = 7.7 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 51.8, 51.9,
124.5, 125.7, 126.8, 127.6, 127.9, 128.4, 128.7, 129.2, 130.1, 130.2, 130.8,
131.4, 131.6, 131.7, 135.1, 137.1, 140.6, 141.3, 167.5, 169.1; HRMS m/z
calcd for C24H20O4 (Mþ) 372.1362, found 372.1365.
Butyl (E)-3-(benzo[b]furan-3-yl)-2-propenoate (17d):11j
.
oil; 1H NMR (400 MHz, CDCl3) δ 0.89 (t, J = 7.3 Hz, 3H),
1.34ꢀ1.40 (m, 2H), 1.59ꢀ1.64 (m, 2H), 4.15 (t, J = 6.9 Hz, 2H),
6.48 (d, J = 16.0 Hz, 1H), 7.25ꢀ7.29 (m, 2H), 7.43ꢀ7.45 (m, 1H), 7.70
(d, J = 16.0 Hz, 1H), 7.76ꢀ7.79 (m, 2H); 13C NMR (100 MHz, CDCl3)
δ 13.7, 19.2, 30.8, 64.4, 111.9, 117.8, 118.4, 121.0, 123.7, 124.7, 125.3,
134.3, 147.7, 156.1, 167.2; HRMS m/z (Mþ) calcd for C15H16O3
244.1099, found 244.1094.
Dimethyl 3,30-distyrylbiphenyl-2,20-dicarboxylate (11):
1
mp 209ꢀ212 °C; H NMR (400 MHz, CDCl3) δ 3.58 (s, 6H), 7.11
(d, J = 16.1 Hz, 2H), 7.20 (d, J = 7.7 Hz, 2H), 7.26ꢀ7.30 (m, 4H), 7.35
(t, J = 7.7 Hz, 4H), 7.42 (t, J = 7.7 Hz, 2H), 7.49 (d, J = 7.7 Hz, 4H), 7.71
(d, J = 7.7 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 51.9, 124.9, 125.6,
126.8, 128.0, 128.67, 128.71, 129.2, 131.9, 132.2, 135.6, 137.0, 139.2,
169.0; HRMS m/z calcd for C32H26O4 (Mþ) 474.1831, found
474.1828.
Butyl (E)-3-(1-methylpyrrol-3-yl)-2-propenoate (17e):11j
.
oil; 1H NMR (400 MHz, CDCl3) δ 0.95 (t, J = 7.3 Hz, 3H),
1.39ꢀ1.45 (m, 2H), 1.62ꢀ1.70 (m, 2H), 3.62 (s, 3H), 4.16 (t, J = 6.6
Hz, 2H), 6.07 (d, J = 15.8 Hz, 1H), 6.35ꢀ6.36 (m, 1H), 6.56ꢀ6.57 (m,
1H), 6.80ꢀ6.81 (m, 1H), 7.58 (d, J = 15.8 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ 13.6, 19.1, 30.8, 36.2, 63.7, 106.8, 112.6, 120.6, 123.7,
124.8, 138.7, 168.1; HRMS m/z (Mþ) calcd for C12H17NO2 207.1259,
found 207.1259.
(E,E)-Methyl 2,5-distyrylbenzoate (13):12. mp 142ꢀ144 °C;
1H NMR (400 MHz, CDCl3) δ 3.94 (s, 3H) 7.01ꢀ7.10 (m, 2H), 7.15
(d, J = 16.5 Hz, 1H), 7.22ꢀ7.28 (m, 2H), 7.33ꢀ7.37 (m, 4H),
7.50ꢀ7.55 (m, 4H), 7.61 (dd, J = 8.2, 1.8 Hz, 1H), 7.70 (d, J = 8.2
Hz, 1H), 7.98 (d, J = 16.0 Hz, 1H), 8.03 (d, J = 1.8 Hz, 1H); 13C NMR
(100 MHz, CDCl3) δ 52.2, 126.6, 126.8 (overlapped), 127.1, 127.2,
127.8, 127.9, 128.6, 128.7, 128.8, 128.9, 129.5, 129.6, 131.2, 136.3, 136.9,
137.4, 138.0, 167.8; HRMS m/z calcd for C24H20O2 (Mþ) 340.1463,
found 340.1456.
Butyl (E)-3-(1-methylindol-3-yl)-2-propenoate (17f):11j. oil;
1H NMR (400 MHz, CDCl3) δ 0.95ꢀ0.99 (m, 3H), 1.42ꢀ1.48 (m,
2H), 1.66ꢀ1.71 (m, 2Hz), 3.72 (s, 3H), 4.18ꢀ4.22 (m, 2H), 6.40 (d, J =
16.0 Hz, 1H), 7.21ꢀ7.30 (m, 4H), 7.84ꢀ7.91 (m, 2H); 13C NMR (100
MHz, CDCl3) δ 13.7, 19.2, 30.9, 33.0, 63.9, 109.8, 111.9, 112.5, 120.5,
121.1, 122.8, 125.9, 133.0, 137.9, 138.0, 168.4; HRMS m/z (Mþ) calcd
for C16H19NO2 257.1416, found 257.1410.
(2Z,4E)-Methyl 2-methyl-5-phenylpenta-2,4-dienoate (15a):23.
oil; 1H NMR (400 MHz, CDCl3) δ 2.02 (s, 3H), 3.79 (s, 3H), 6.59 (d,
J = 11.7 Hz, 1H), 6.68 (d, J = 16.1 Hz, 1H), 7.24ꢀ7.33 (m, 3H), 7.47 (d,
J = 7.7 Hz, 2H), 7.90 (dd, J = 11.7, 16.1 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 20.9, 51.4, 125.9, 126.0, 127.1, 128.3, 128.6, 136.8, 138.2,
140.8, 167.9; HRMS m/z (Mþ) calcd for C13H14O2 202.0994, found
202.0990.
’ ASSOCIATED CONTENT
1
Supporting Information. Copies of H and 13C NMR
S
b
spectra of products. This material is available free of charge via
the Internet at http://pubs.acs.org.
(2Z,4E)-Methyl 2-methyl-5-(naphthalen-2-yl)penta-2,4-die-
1
noate (15b): mp 80ꢀ82 °C; H NMR (400 MHz, CDCl3) δ 2.05
(s, 3H), 3.82 (s, 3H), 6.64 (d, J = 11.5 Hz, 1H), 6.84 (d, J = 15.6 Hz, 1H),
7.43ꢀ7.47 (m, 2H), 7.68ꢀ7.70 (m, 1H), 7.77ꢀ7.80 (m, 4H), 8.04 (dd,
J = 11.5, 15.6 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 20.9, 51.5, 123.8,
126.0, 126.21, 126.24, 126.3, 127.5, 127.7, 128.1, 128.3, 133.4, 133.5,
134.4, 138.4, 141.0, 168.0; HRMS m/z (Mþ) calcd for C17H16O2
252.1150, found 252.1151.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: satoh@chem.eng.osaka-u.ac.jp; miura@chem.eng.osaka-u.
ac.jp.
(2Z,4E)-Methyl 2,3-dimethyl-5-(naphthalen-2-yl)penta-
1
2,4-dienoate (15c): mp 78ꢀ79 °C; H NMR (400 MHz, CDCl3)
’ ACKNOWLEDGMENT
δ 2.05 (s, 3H), 2.07 (s, 3H), 3.83 (s, 3H), 6.92 (d, J = 16.0 Hz, 1H),
7.41ꢀ7.45 (m, 2H), 7.66ꢀ7.69 (m, 1H), 7.76ꢀ7.81 (m, 4H), 7.92 (d,
J = 16.0 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 15.5, 16.9, 51.7, 123.7,
125.9, 126.2, 126.3, 127.1, 127.6, 128.0, 128.2, 128.6, 131.5, 133.1, 133.6,
134.9, 140.9, 169.8; HRMS m/z (Mþ) calcd for C18H18O2 266.1307,
found 266.1303.
This work was partly supported by Grants-in-Aid from MEXT
and JSPS, Japan.
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3031
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FEATURED ARTICLE
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