Cp?Co(III)-catalyzed oxidative C-H alkenylation of benzamides with ethyl acrylate

Article abstract of DOI:10.1016/j.tet.2015.02.032

The utility of Cp^?Co(III)-catalysts was expanded to oxidative C-C bond-forming reaction. In situ-generated Cp^?Co(III)-catalyst, rather than a preformed cationic Cp^?Co(III)-complex, was effective. Oxidative alkenylation of benzamides and acetanilide with ethyl acrylate proceeded with silver acetate as a stoichiometric oxidant, giving products in up to 93% yield.

Full text of DOI:10.1016/j.tet.2015.02.032

Accepted Manuscript
Cp*Co(III)-catalyzed oxidative C-H alkenylation of benzamides with ethyl acrylate
Yudai Suzuki, Bo Sun, Tatsuhiko Yoshino, Motomu Kanai, Shigeki Matsunaga
PII:
S0040-4020(15)00167-2
10.1016/j.tet.2015.02.032
TET 26421
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 21 January 2015
Accepted Date: 7 February 2015
Please cite this article as: Suzuki Y, Sun B, Yoshino T, Kanai M, Matsunaga S, Cp*Co(III)-catalyzed
oxidative C-H alkenylation of benzamides with ethyl acrylate, Tetrahedron (2015), doi: 10.1016/
j.tet.2015.02.032.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Cp*Co(III)-catalyzed oxidative C-H
alkenylation of benzamides with ethyl
acrylate
Leave this area blank for abstract info.
Yudai Suzuki, Bo Sun, Tatsuhiko Yoshino, Motomu Kanai* and Shigeki Matsunaga *

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Cp*Co(III)-catalyzed oxidative C-H alkenylation of benzamides with ethyl acrylate
Yudai Suzukia, Bo Suna, Tatsuhiko Yoshinoa,b, Motomu Kanaia,* and Shigeki Matsunagaa,b,c
*
aGraduate School of Pharmaceutical Sciences, the University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, Japan, 113-0033
bACT-C, Japan Science and Technology Agency (JST), 7-3-1 Hongo, Bunkyo-ku, Tokyo, Japan, 113-0033
cFaculty of Pharmaceutical Sciences, Hokkaido University, Sapporo, Japan, 060-0812
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
The utility of Cp*Co(III)-catalysts was expanded to oxidative C-C bond-forming reaction. In
situ-generated Cp*Co(III)-catalyst, rather than a preformed cationic Cp*Co(III)-complex, was
effective. Oxidative alkenylation of benzamides and acetanilide with ethyl acrylate proceeded
with silver acetate as a stoichiometric oxidant, giving products in up to 93% yield.
Available online
2015 Elsevier Ltd. All rights reserved
.
Cobalt
Oxidative cou Keywords:
Alkenylation
Catalysis
C-H activation
pling
reactions9b as well as in some formally nucleophilic substitution
reactions.10b On the other hand, there are no reports of oxidative
C-C bond-forming reactions with external oxidants under
1. Introduction
Functionalization of ubiquitous unreactive C-H bonds has
attracted considerable attention in the field of organic synthesis.1
The C-H functionalization process provides new opportunities
for developing atom-2 and step-economical3 synthetic routes of
natural products, biologically active compounds, functional
organic materials, and other useful organic molecules. Regio- and
chemoselective activation of a specific C-H bond among
numerous C-H bonds in a molecule is essential for this purpose.
Directing group-assisted C-H bond activation under transition
metal catalysis is the most successful and widely used strategy,
and various catalysts have been developed over the last two
decades. Among them, cationic Cp*Rh(III) complexes are widely
applied for various oxidative as well as redox neutral C-C, C-N,
and other C-X bond-forming reactions.4 Despite their high
catalytic activity and broad reaction scope, however, the use of
expensive rhodium metal has disadvantages for future application
in large-scale synthesis. Thus, the development of an alternative
catalyst with readily available base metal sources is highly
desirable.5-7 Since our report on the utility of a cationic
Cp*Co(III)-arene complex 1a in 2013 (Fig. 1),8 we and others
have attempted to broaden the scope of Cp*Co(III)-catalysis.9,10
Cp*Co(III) complexes were successfully applied for a variety of
redox neutral C-C and C-N bond formations. Cp*Co(III) was
found to be superior to Cp*Rh(III) in some nucleophilic addition
Cp*Co(III)-catalysis.11
Studies
of
oxidative
C-H
functionalizations are, therefore, important toward broadening
the scope of Cp*Co(III)-catalysis. Herein, we demonstrate
oxidative alkenylation of arenes with ethyl acrylate. The
appropriate cationic Cp*Co(III) complex promoted the
alkenylation reaction in the presence of silver oxidant, affording
products in up to 93% yield.
Me
Co
Me
Co
Me
Me
Me
Me
Me
Me
(PF6)2
Me
Me
CO
I
I
1a
1b
Fig. 1. Structures of Cp*Co(III)-complexes 1a and 1b.
2. Results and discussion
Transition metal-catalyzed oxidative alkenylation reactions of
arenes, especially those using Pd, Rh, and Ru-catalysts, have
been studied extensively.12,13 Thus, we selected the reaction of
arenes and acrylate as a model reaction to evaluate the feasibility
———
*
Corresponding author. Tel.: +81-3-5841-4836; fax: +81-3-5684-5206; e-mail: kanai@mol.f.u-tokyo.ac.jp; smatsuna@mol.f.u-tokyo.ac.jp

2
Tetrahedron
ACCEPTED MANUSCRIPT
of oxidative C-C bond-forming processes under Cp*Co(III)-
benzamides is summarized in Table 2. Various functional groups
catalysis. Optimization studies of benzamide 2a and ethyl
acrylate 3 are summarized in Table 1. Our original cationic
Cp*Co(III)-arene complex 1a gave trace, if any, amounts of the
desired product 4a in the presence of silver acetate as a
stoichiometric oxidant (entry 1). On the other hand, in situ-
generated Co(III)-catalyst by mixing Cp*Co(CO)I2 1b and
AgPF6 gave the product in 54% yield. The selection of the
counter ion affected the reactivity of the Co(III)-catalyst, and
AgSbF6 afforded the best reactivity among silver salts screened
(entries 2-6). The results were not improved by the use of any
other oxidants screened. The use of benzoquinone as an oxidant
led to only trace amounts of the product (entry 7). Cu(OAc)2,
which is often used for oxidative reactions under Cp*Rh(III)-
catalysis, resulted in a lower yield than AgOAc (entry 8, 48%).
We assume that the selection of a suitable oxidant is important
for efficient catalyst turnover to regenerate catalytically active
Cp*Co(III), while suppressing undesirable catalyst de-activation
from the relatively unstable Cp*Co(I) species. Ag2CO3 also
resulted in a low yield (entry 9, 16%), possibly because the
acetate ion is important to efficiently assist the C-H activation
step. The reaction proceeded smoothly even at 40 °C, but resulted
in a slightly lower yield (entry 10, 73%). Thus, we selected the
conditions in entry 6 as optimum for oxidative alkenylation.
Negative control experiments in entries 11-15 suggested that the
use of the well-defined cationic Cp*Co(III)-catalyst is required
for present C-H functionalization.
at the para-position, such as Me, MeO, F, Br, CF3, NO2, and
CO2Me, were compatible (4b-4h, 73-93%), while phenol and
aniline units (4i and 4j) gave complex mixtures of byproducts.
Substituents at the meta-position also gave the products in good
yield (4k and 4l). Good regioselectivity with meta-substituted
substrates can be explained based on the steric factor. C-H
metalation occurred selectively at the sterically less hindered
position. With an ortho-substituted substrate, the reactivity
decreased significantly, and product 4m was obtained in only
33% yield. The ortho-substituent would destabilize a planar
metalacyclic intermediate due to steric repulsion. In addition to
other benzamide derivatives 4n and 4o, the C-H bond of
thiophenyl unit was also functionalized, albeit in moderate yield
(4p, 52%). As shown in Scheme 1, acetanilide (5) also reacted
with ethyl acrylate, although 20 mol % of Cp*Co(III) was
required to obtain product 6 in 61% yield.
Table 2. Cp*Co(III)-catalyzed oxidative alkenylation of
benzamides.a
Table 1. Optimization studies of Cp*Co(III)-catalyzed oxidative
alkenylation.
a
Reaction was run using 4 (0.10 mmol) and 3 (0.15 mmol).
Isolated yields of 4 after purification by silica gel column
chromatography are shown in Table 2.
1
a Yield of 4a determined by H NMR analysis of crude mixture
with an internal standard.
Scheme 1. Cp*Co(III)-catalyzed oxidative alkenylation of
acetanilide 5.
b
Isolated yield of 4a after purification by silica gel column
A plausible catalytic cycle is shown in Fig. 2. Initial halide
abstraction from Cp*Co(CO)I2 1b by AgSbF6 in the presence of
the AgOAc would form a neutral Cp*Co(III)(OAc)2 complex,
which would be a resting complex. On the basis of our previous
mechanistic studies,9b we speculate that mono-cationic
[Cp*Co(III)(OAc)]+ I would be a catalytically active species. We
chromatography.
We then investigated the scope and limitations of Cp*Co(III)-
catalyzed oxidative alkenylation reactions. The scope of

3
assume that the concentration of the catalytically active species
would be different depending on silver salts, which led to the
reactivity difference observed in Table 1, entries 2-6. A key C-H
bond activation step to afford metalacycle II would proceed via
concerted metalation-deprotonation (CMD)14 assisted by the
acetate ion. Insertion into acrylate (III), followed by β-hydride
elimination and reductive elimination, would afford product 4,
AcOH, and Cp*Co(I). Oxidation of Cp*Co(I) by silver salt
regenerated the Cp*Co(III)-catalyst.
1H); 13C NMR (CDCl3, 100 MHz) δ 14.4, 27.0, 60.7, 120.9,
ACCEPTED MANUSCRIPT
127.2, 127.7, 129.9, 130.4, 132.8, 137.3, 141.9, 166.6, 169.5;
+
HRMS (ESI): m/z calculated for C13H15NNaO3
[M+Na]+:
256.0944, found: 256.0956.
4.1.2. (E)-Ethyl 3-(5-methyl-2-
(methylcarbamoyl)phenyl)acrylate (4b).
A colorless solid; IR (KBr) ν 2982, 1714, 1643, 1550, 1317,
1178, 1037, 976, 862 cm-1; 1H NMR (CDCl3, 400 MHz) δ 1.32 (t,
J = 5.5 Hz , 3 H), 2.38 (s, 3H), 3.00 (d, J = 4.1 Hz, 3H), 4.23 (q, J
= 5.5 Hz, 2H), 5.78 (brs, 1H), 6.36 (d, J = 12.4 Hz, 1H), 7.19 (d,
J = 6.4 Hz, 1H), 7.34-7.42 (m, 2H), 8.00 (d, J = 12.4 Hz, 1H);
13C NMR (CDCl3, 100 MHz) δ 14.4, 21.4, 27.0, 60.7, 120.7,
127.8, 127.8, 130.6, 132.9, 134.5, 140.5, 142.3, 166.7, 169.5;
+
HRMS (ESI): m/z calculated for C14H17NNaO3
[M+Na]+:
270.1101, found: 270.1092.
4.1.3. (E)-Ethyl 3-(5-methoxy-2-
(methylcarbamoyl)phenyl)acrylate (4c).
A colorless solid; IR (KBr) ν 2985, 2942, 1715, 16641, 1625,
1
1546, 1314, 1293, 1228, 1182, 1034, 974, 862 cm-1; H NMR
(CDCl3, 400 MHz) δ 1.32 (t, J = 7.3 Hz , 3 H), 2.98 (d, J = 5.0
Hz, 3H), 3.83 (s, 3H), 4.24 (q, J = 7.3 Hz, 2H), 5.88 (brs, 1H),
6.33 (d, J = 16.7 Hz, 1H), 6.89 (dd, J = 2.3, 8.7 Hz, 1H), 7.06 (d,
J = 2.3 Hz, 1H), 7.43 (d, J = 8.7 Hz, 1s) 8.02 (d, J = 16.5 Hz,
1H); 13C NMR (CDCl3, 100 MHz) δ 14.4, 27.1, 55.6, 60.8,
112.2, 115.4, 121.1, 129.5, 129.7, 135.0, 142.3, 161.0, 166.6,
Fig. 2. Plausible catalytic cycle.
+
169.2; HRMS (ESI): m/z calculated for C14H17NNaO4 [M+Na]+:
286.1050, found: 286.1054.
3. Conclusion
In conclusion, we report the first successful application of a
Cp*Co(III)-catalyst to oxidative C-H alkenylation with an
external oxidant, thereby expanding the utility of Cp*Co(III)-
catalysis. The present protocol can be further improved, however,
with regard to the use of precious silver salt as a stoichiometric
oxidant and the limited substrate scope. Additional studies to
improve the Cp*Co(III)-catalyzed oxidative process, including
the use of environmentally benign oxidant, are ongoing in our
group.
4.1.4. (E)-Ethyl 3-(5-fluoro-2-
(methylcarbamoyl)phenyl)acrylate (4d).
A colorless solid; IR (KBr) ν 3082, 2984, 1721, 1635, 1558,
1321, 1182, 1034, 971, 855 cm-1; 1H NMR (CDCl3, 400
MHz) δ 1.30 (t, J = 6.8 Hz , 3 H), 2.99 (d, J = 5.0 Hz, 3H), 4.24
(q, J = 6.8 Hz, 2H), 5.95 (brs, 1H), 6.34 (d, J = 16.5 Hz, 1H),
7.04 (ddd, J = 2.8, 8.7, 8.7 Hz, 1H), 7.25 (dd, J = 2.8, 10.1 Hz,
1H), 7.44 (dd, J = 6.0, 8.7 Hz, 2H), 7.91 (d, J = 16.5 Hz, 1H); 13C
NMR (CDCl3, 100 MHz) δ 14.4, 27.1, 60.9, 113.9 (d, J = 22.9
Hz), 116.8 (d, J = 22.9 Hz), 122.1, 130.6 (d, J = 9.5 Hz), 133.4
(d, J = 2.9 Hz), 135.5 (d, J = 7.6 Hz), 140.8 (d, J = 2.9 Hz), 163.5
(d, J = 254.7 Hz), 166.3, 168.6; HRMS (ESI): m/z calculated for
4. Experimental Section
4.1. General Procedure (Table 2)
+
C13H14FNNaO3 [M+Na]+: 274.0850, found: 274.0844.
To a dried screw-capped vial were added benzamide 2 (0.10
mmol), ethyl acrylate 3 (0.15 mmol), 1b (4.8 mg, 0.01 mmol),
AgSbF6 (6.8mg, 0.02 mmol), AgOAc (41.7 mg, 0.25 mmol) and
1,2-dichloroethane (1.0 mL) under Ar atmosphere. The vial was
capped and the mixture was heated at 60 °C for 13 h with
stirring. After the mixture was cooled to room temperature,
saturated EDTA·2Na aq. was added following dilution with
4.1.5. (E)-Ethyl 3-(5-bromo-2-
(methylcarbamoyl)phenyl)acrylate (4e).
A colorless solid; IR (KBr) ν 3079, 2975, 2935, 1719, 1642,
1561, 1316, 1190, 1032, 979, 862 cm-1; H NMR (CDCl3, 400
1
MHz) δ 1.32 (t, J = 7.5 Hz , 3 H), 3.00 (d, J = 5.2 Hz, 3H), 4.23
(q, J = 7.5 Hz, 2H), 5.88 (brs, 1H), 6.36 (d, J = 16.0 Hz, 1H),
7.34 (d, J = 8.6 Hz, 1H), 7.49 (d, J = 8.6 Hz, 1H), 7.74 (s, 1H)
7.90 (d, J = 16.0 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 14.4,
27.1, 60.1, 122.1, 124.1, 124.7, 129.3, 130.1, 132.7, 134.9, 135.8,
140.5, 166.2, 168.5; HRMS (ESI): m/z calculated for
CH
extracted with CH
over Na SO . After filtration and evaporation, obtained crude
mixture was purified by silica gel column chromatography
(CH Cl /EtOAc) to give product 3.
2
Cl
2
. Organic layer was separated and aqueous layer was
2
Cl2 (x 2). Combined organic layers were dried
2
4
2
2
+
C13H14BrNNaO3 [M+Na]+: 334.0049, found: 334.0050.
4.1.1. (E)-Ethyl 3-(2-
(methylcarbamoyl)phenyl)acrylate (4a).
4.1.6. (E)-Ethyl 3-(2-(methylcarbamoyl)-5-
(trifluoromethyl)phenyl)acrylate (4f).
A colorless solid; IR (KBr) ν 3085, 2979, 1714, 1703, 1635,
1557, 1270, 1048, 980, 767 cm-1; 1H NMR (CDCl3, 400
MHz) δ 1.31 (t, J = 7.3 Hz , 3 H), 2.99 (d, J = 4.6 Hz, 3H), 4.23
(q, J = 7.3 Hz, 2H), 5.98 (brs, 1H), 6.35 (d, J = 16.0 Hz, 1H),
7.34-7.50 (m, 3H), 7.59 (s, J = 7.3 Hz, 1H), 7.96 (d, J = 16.0 Hz,
A colorless solid; IR (KBr) ν 3084, 2974, 1717, 1642, 1551,
1337, 1292, 1159, 1122, 1042, 989, 924, 843 cm-1; H NMR
1
(CDCl3, 400 MHz) δ 1.33 (t, J = 6.9 Hz , 3 H), 3.04 (d, J = 4.6
Hz, 3H), 4.24 (q, J = 6.9 Hz, 2H), 5.88 (brs, 1H), 6.45 (d, J =

4
Tetrahedron
ACCEPTED MANUSCRIPT
16.0 Hz, 1H), 7.57-7.65 (m, 2H), 7.85 (s, 1H) 7.94 (d, J = 16.0
MHz) δ 1.31 (t, J = 7.3 Hz , 3 H), 2.34 (s, 3H), 3.04 (d, J = 5.0
Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 14.4, 27.1, 61.0, 122.6,
123.5 (q, J = 273.4 Hz), 124.1 (q, J = 3.8 Hz), 126.3 (q, J = 22.9
Hz), 128.4, 132.5 (q, J = 32.9 Hz), 133.7; HRMS (ESI): m/z
calculated for C14H14F3NNaO3
324.0818.
Hz, 3H), 4.22 (q, J = 7.3 Hz, 2H), 5.72 (brs, 1H), 6.38 (d, J =
16.0 Hz, 1H), 7.21 (d, J = 7.8 Hz, 1H), 7.28 (dd, J = 7.8, 7.8 Hz,
1H), 7.70 (d, J = 16.0 Hz, 1H); 13C NMR (CDCl3, 100 MHz)
δ 14.4, 19.3, 26.8, 60.7, 120.8, 124.0, 1293, 131.7, 121.9, 135.6,
138.2, 141.6, 166.7, 169.8; HRMS (ESI): m/z calculated for
[M+Na]+: 324.0818, found:
+
C14H17NNaO3 [M+Na]+: 270.1101, found: 270.1102.
+
4.1.7. (E)-Ethyl 3-(2-(methylcarbamoyl)-5-
nitrophenyl)acrylate (4g).
4.1.12. (E)-Ethyl 3-(3-
(methylcarbamoyl)naphthalen-2-yl)acrylate (4n).
A colorless solid; IR (KBr) ν 3085, 2977, 1713, 1643, 1556,
1
1522, 1352, 1282, 1040, 989, 825 cm-1; H NMR (CDCl3, 400
A colorless solid; IR (KBr) ν 2981, 1715, 1644, 1622, 1551,
1
MHz) δ 1.31 (t, J = 7.3 Hz , 3 H), 3.03 (d, J = 5.0 Hz, 3H), 4.26
(q, J = 7.3 Hz, 2H), 6.14 (brs, 1H), 6.50 (d, J = 16.5 Hz, 1H),
7.62 (d, J = 8.7 Hz, 1H), 7.89 (d, J = 16.5 Hz, 1H), 8.19 (d, J =
8.7 Hz, 1H) 8.43 (s, 1H); 13C NMR (CDCl3, 100 MHz) δ 14.4,
27.2, 61.2, 122.1, 123.7, 124.2, 134.7, 139.4, 142.3, 148.8, 165.9,
1304, 1177, 1033, 976, 863, 758 cm-1; H NMR (CDCl3, 400
MHz) δ 1.33 (t, J = 7.3 Hz , 3 H), 3.05 (d, J = 5.0 Hz, 3H), 4.26
(q, J = 7.3 Hz, 2H), 6.14 (brs, 1H), 6.44 (d, J = 16.5 Hz, 1H),
7.50-7.57 (m, 2H), 7.76-7.87 (m, 2H), 7.91 (s, 1H), 8.01 (s, 1H),
8.23 (d, J = 16.5 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 14.5,
27.1, 60.7, 120.8, 127.6, 127.7, 127.8, 127.9, 128.2, 128.4, 130.4,
+
167.5; HRMS (ESI): m/z calculated for C13H14N2NaO5
[M+Na]+: 301.0795, found: 301.0791.
133.0, 133.6, 134.4, 142.5, 166.7, 169.5; HRMS (ESI): m/z
+
calculated for C17H17NNaO3
306.1105.
[M+Na]+: 306.1101, found:
4.1.8. (E)-Methyl 3-(3-ethoxy-3-oxoprop-1-en-1-yl)-
4-(methylcarbamoyl)benzoate (4h).
4.1.13. (E)-Ethyl 3-(2-(tert-
butylcarbamoyl)phenyl)acrylate (4o).
A colorless solid; IR (KBr) ν 3082, 2988, 2954, 1721, 1644,
1
1551, 1320, 1252, 1184, 1032, 976, 866, 760 cm-1; H NMR
(CDCl3, 400 MHz) δ 1.32 (t, J = 7.2 Hz , 3 H), 3.02 (d, J = 4.8
Hz, 3H), 3.94 (s, 3H), 4.25 (q, J = 7.2 Hz, 2H), 6.07 (brs, 1H),
6.46 (d, J = 16.0 Hz, 1H), 7.50 (d, J = 7.6 Hz, 1H), 7.92 (d, J =
16.0 Hz, 1H), 7.99 (d, J = 7.6 Hz, 1H), 8.35 (s, 1H); 13C NMR
(CDCl3, 100 MHz) δ 14.4, 27.1, 52.7, 60.9, 122.1, 122.1, 127.9,
A colorless oil; IR (neat) ν 3063, 2971, 1712, 1639, 1538, 1314,
1
1177, 1094, 1042, 977, 879, 764 cm-1; H NMR (CDCl3, 400
MHz) δ 1.33 (t, J = 7.3 Hz , 3 H), 1.49 (s, 9H), 4.26 (q, J = 7.3
Hz, 2H), 5.55 (brs, 1H), 6.39 (d, J = 16.0 Hz, 1H), 7.36-7.50 (m,
3H), 7.59 (s, J = 7.4 Hz, 1H), 7.98 (d, J = 16.0 Hz, 1H); 13C
NMR (CDCl3, 100 MHz) δ 14.4, 28.9, 52.4, 60.7, 120.8, 127.0,
127.7, 130.0, 130.1, 132.3, 138.7, 142.0, 166.6, 168.3; HRMS
128.4, 130.6, 131.9, 133.2, 140.8, 140.9, 166.0, 166.4, 168.6;
+
HRMS (ESI): m/z calculated for C15H17NNaO5
[M+Na]+:
+
314.0999, found: 314.0993.
(ESI): m/z calculated for C16H20BrNNaO3 [M+Na]+: 298.1414,
found: 298.1423.
4.1.9. (E)-Ethyl 3-(4-methyl-2-
(methylcarbamoyl)phenyl)acrylate (4k).
4.1.14. (E)-Ethyl 3-(2-(methylcarbamoyl)thiophen-
3-yl)acrylate (4p).
A colorless solid; IR (KBr) ν 2979, 1715, 1639, 1604, 1541,
1
1309, 1272, 1178, 1030, 977, 822 cm-1; H NMR (CDCl3, 400
A colorless solid; IR (neat) ν 2979, 1707, 1632, 1536, 1244,
1178, 1037, 987, 867, 774 cm-1; 1H NMR (CDCl3, 400
MHz) δ 1.33 (t, J = 6.9 Hz , 3 H), 3.01 (s, 3H), 4.26 (q, J = 6.9
Hz, 2H), 6.33 (d, J = 16.5 Hz, 1H), 5.84 (brs, 1H), 7.29 (d, J =
5.5 Hz, 1H), 7.33 (d, J = 5.5 Hz, 1H), 8.26 (d, J = 16.5 Hz, 1H);
13C NMR (CDCl3, 100 MHz) δ 14.5,27.2, 60.8, 121.7, 127.0,
127.2, 136.4, 136.5, 138.6, 162.8, 162.9; HRMS (ESI): m/z
calculated for C11H13NNaO3S+ [M+Na]+: 262.0508, found:
262.0513.
MHz) δ 1.30 (t, J = 7.3 Hz , 3 H), 2.35 (s, 3H), 3.00 (d, J = 5.0
Hz, 3H), 4.22 (q, J = 7.3 Hz, 2H), 5.88 (brs, 1H), 6.32 (d, J =
16.0 Hz, 1H), 7.29-7.37 (m, 2H), 7.48 (d, J = 8.2 Hz, 1H), 7.92
(d, J = 16.0 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 14.4, 21.4,
27.0, 60.7, 119.9, 127.2, 128.4, 129.9, 131.1, 137.3, 140.4, 141.8,
+
166.8, 169.6; HRMS (ESI): m/z calculated for C14H17NNaO3
[M+Na]+: 270.1101, found: 270.1104.
4.1.10. (E)-Ethyl 3-(4-bromo-2-(tert-
butylcarbamoyl)phenyl)acrylate (4l).
4.1.15. (E)-Ethyl 3-(2-acetamidophenyl)acrylate (6)
(Scheme 2).
A colorless oil; IR (neat) ν 3065, 2973, 1714, 1641, 1541, 1312,
1
1263, 1178, 1097, 1041, 976, 895, 816 cm-1; H NMR (CDCl3,
To a dried screw-capped vial were added acetanilide 5 (0.10
mmol), ethyl acrylate 3 (0.15 mmol), 1b (9.6 mg, 0.02 mmol),
AgSbF6 (13.6mg, 0.04 mmol), AgOAc (41.7 mg, 0.25 mmol) and
1,2-dichloroethane (1.0 mL) under Ar atmosphere. The vial was
capped and the mixture was heated at 60 °C for 13 h with
stirring. After the mixture was cooled to room temperature,
saturated EDTA·2Na aq. was added following dilution with
400 MHz) δ 1.31 (t, J = 7.3 Hz , 3 H), 1.47(s, 9H), 4.24 (q, J =
7.3 Hz, 2H), 5.64 (brs, 1H), 6.35 (d, J = 16.5 Hz, 1H), 7.43 (d, J
= 7.8 Hz, 1H), 7.52 (dd, J = 2.3, 7.8 Hz, 1H), 7.57 (s, J = 2.3 Hz,
1H), 7.85 (d, J = 16.5 Hz, 1H); 13C NMR (CDCl3, 100 MHz)
δ 14.4, 28.8, 52.7, 60.8, 121.3,124.0, 128.5, 130.7, 131.2, 133.1,
140.0, 140.7, 166.3, 166.7; HRMS (ESI): m/z calculated for
+
C16H20BrNNaO3 [M+Na]+: 376.0519, found: 376.0520.
CH
extracted with CH
over Na SO . After filtration and evaporation, obtained crude
mixture was purified by silica gel column chromatography
(CH Cl /EtOAc) to give product 6. A colorless solid; IR (KBr) ν
2
Cl
2
. Organic layer was separated and aqueous layer was
2
Cl2 (x 2). Combined organic layers were dried
2
4
4.1.11. (E)-Ethyl 3-(3-methyl-2-
(methylcarbamoyl)phenyl)acrylate (4m).
2
2
2978, 1712, 1659, 1537, 1455, 1302, 1270, 1045, 971, 764, 743
A colorless oil; IR (neat) ν 2980, 1710, 1638, 1543, 1313, 1233,
1
cm-1; H NMR (CDCl3, 400 MHz) δ 1.33 (t, J = 7.6 Hz , 3 H),
1090, 1039, 979, 867, 790 cm-1; 1H NMR (CDCl3, 400

5
10. (a) Li, J.; Ackerman, L. Angew. Chem. Int. Ed., Early View,
2.23 (s, 3H), 4.26 (q, J = 7.6 Hz, 2H), 6.39 (d, J = 16.0 Hz, 1H),
7.20 (m, 1H), 7.29-7.43 (m, 2H), 7.54 (d, J = 7.6 Hz, 1H), 7.70-
7.90 (m, 2H); 13C NMR (CDCl3, 100 MHz) δ 14.4, 24.4, 60.9,
120.9, 125.3, 126.0, 127.3, 127.7, 130.9, 136.0, 139.4, 166.9,
ACCEPTED MANUSCRIPT
[DOI: 10.1002/anie.201409247]; (b) Yu, D.-G.; Gensch, T.; de
Azambuja, F.; Vásquez-Céspedes, S.; Glorius, F. J. Am. Chem.
Soc. 2014, 136, 17722. (c) Hummel, J. R.; Ellman, J. A. J. Am.
Chem. Soc., ASAP article, [DOI: 10.1021/ja5116452]. (d) Patel,
P.; Chang, S. ACS Catal. 2015, 5, 853.
+
169.0; HRMS (ESI): m/z calculated for C13H15NNaO3 [M+Na]+:
11. For Co(OAc)2-catalyzed oxidative C-H alkenylation using an
aminoquinoline directing group, see: (a) Grigorjeva, L.; Daugulis,
O. Angew. Chem. Int. Ed. 2014, 53, 10209. See also, (b)
Grigorjeva, L.; Daugulis, O. Org. Lett. 2014, 16, 4684.
256.0944, found: 256.0936
12. For selected reviews on oxidative C-H alkenylation, see: (a)
Moritani, I.; Fujiwara, Y. Synthesis 1973, 524. (b) Jia, C.;
Kitamura, T.; Fujiwara, Y. Acc. Chem. Res. 2001, 34, 633. (c)
Ritleng, V.; Sirlin, C.; Preffer, M. Chem. Rev. 2002, 102, 1731. (d)
Beccalli, E. M.; Broggini, G.; Martinelli, M.; Sottocornola, S.
Chem. Rev. 2007, 107, 5318. (e) Chen, X.; Engle, K. M.; Wang,
D.-H.; Yu, J.-Q. Angew. Chem. Int. Ed. 2009, 48, 5094. (f) Karimi,
B.; Behzadnia, H.; Elhamifar, D.; Akhavan, P. F.; Esfahani, F. K.;
Zamani, A. Synthesis 2010, 1399. (g) Engle, K. M.; Yu, J.-Q. J.
Org. Chem. 2013, 78, 8927.
Acknowledgments
This work was supported by ACT-C from JST, Grant-in-Aid
for Scientific Research on Innovative Areas from MEXT and the
Naito foundation. Y.S. thanks JSPS fellowship.
References and notes
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Sci.
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Lapointe, K. Fagnou, Chem. Lett. 2010, 39, 1118. (b) Ackermann,
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Yoshikai, N. Bull. Chem. Soc. Jpn. 2014, 87, 1047.
Supplementary Material
7. Low-valent cobalt catalysts have been intensively investigated for
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Gao, K.; Lee, P.-S.; Fujita, T.; Yoshikai, N. J. Am. Chem. Soc.
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Supplementary data associated with this article can be found
in the online version, at http://dx.doi.org/10.1016/j.tet.xxxxxxxxx
8. Yoshino, T.; Ikemoto, H.; Matsunaga, S.; Kanai, M. Angew.
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9. (a) Yoshino, T.; Ikemoto, H.; Matsunaga, S.; Kanai, M. Chem.
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Sun, B.; Yoshino, T.; Matsunaga, S.; Kanai, M. Adv. Synth. Catal.
2014, 356, 1491.

ACCEPTED MANUSCRIPT
Supplementary Material
Cp*Co(III)-catalyzed oxidative C-H alkenylation of benzamides with ethyl acrylate
Yudai Suzuki, Bo Sun, Tatsuhiko Yoshino, Motomu Kanai* and Shigeki Matsunaga *
Experimental Section
General: Infrared (IR) spectra were recorded on a JASCO FT/IR 410 Fourier transform infrared
spectrophotometer. NMR spectra were recorded on JEOL JNM-ECS400 spectrometers, operating at 400
MHz for 1H NMR and 98.52 MHz for 13C NMR. Chemical shifts in CDCl3 was reported in the scale relative
1
13
to CHCl3 (7.26 ppm for H NMR) and CDCl3 (77.16 ppm for C NMR) as an internal reference. ESI mass
spectra for HRMS were measured on a JEOL JMS-T100LC AccuTOF spectrometer. Column
chromatography was performed with silica gel Merck 60 (230−400 mesh ASTM). 1,2-Dichloroethane
(DCE) was distilled from CaH2, purged with argon for over 30 min and stored over activated
molecular sieves 4A under argon atmosphere. Cp*Co(CO)I2 was synthesized according to the
literature.[1] All benzamides 2 were prepared by the same procedure as described in the literature.[2,3]
Acetanilide was purchased from Aldrich and used without purification. Commercially available
ethyl acrylate (TCI) was purified by distillation before use.
[1] Sun, B.; Yoshino, T.; Matsunaga, S.; Kanai, M. Adv. Synth. Catal. 2014, 356, 1491.
[2] Ackermann, L.; Wang, L.; Wolfram, R.; Lygin, A.V. Org. Lett. 2012, 14, 728.
[3] Ryu, J.; Shin, K.; Park, S. H.; Kim, J. Y.; Chang, S. Angew. Chem. Int. Ed. 2012, 51, 9904
General Procedure of Cobalt(III)-Catalyzed Alkenylation
To a dried screw-capped vial were added benzamide 2 (0.10 mmol), ethyl acrylate 3 (0.15 mmol), 1b (4.8 mg,
0.01 mmol), AgSbF6 (6.8mg, 0.02 mmol), AgOAc (41.7 mg, 0.25 mmol) and 1,2-dichloroethane (1.0 mL)
under Ar atmosphere. The vial was capped and the mixture was heated at 60 °C for 13 h with stirring. After
the mixture was cooled to room temperature, saturated EDTA·2Na aq. was added following dilution with
CH2Cl2. Organic layer was separated and aqueous layer was extracted with CH2Cl2 (x 2). Combined organic
layers were dried over Na2SO4. After filtration and evaporation, obtained crude mixture was purified by
silica gel column chromatography (CH2Cl2/EtOAc) to give a corresponding product 3.
(E)-ethyl 3-(2-(methylcarbamoyl)phenyl)acrylate (4a): a colorless solid; IR (KBr)
1
ν 3085, 2979, 1714, 1703, 1635, 1557, 1270, 1048, 980, 767 cm-1; H NMR (CDCl3,
400 MHz) δ 1.31 (t, J = 7.3 Hz , 3 H), 2.99 (d, J = 4.6 Hz, 3H), 4.23 (q, J = 7.3 Hz,
2H), 5.98 (brs, 1H), 6.35 (d, J = 16.0 Hz, 1H), 7.34-7.50 (m, 3H), 7.59 (s, J = 7.3 Hz,
1H), 7.96 (d, J = 16.0 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 14.4, 27.0, 60.7, 120.9, 127.2, 127.7, 129.9,
S-1

ACCEPTED MANUSCRIPT
130.4, 132.8, 137.3, 141.9, 166.6, 169.5; HRMS (ESI): m/z calculated for C13H15NNaO3 [M+Na]+:
+
256.0944, found: 256.0956
(E)-ethyl 3-(5-methyl-2-(methylcarbamoyl)phenyl)acrylate (4b): a colorless
1
solid; IR (KBr) ν 2982, 1714, 1643, 1550, 1317, 1178, 1037, 976, 862 cm-1; H
NMR (CDCl3, 400 MHz) δ 1.32 (t, J = 5.5 Hz , 3 H), 2.38 (s, 3H), 3.00 (d, J =
4.1 Hz, 3H), 4.23 (q, J = 5.5 Hz, 2H), 5.78 (brs, 1H), 6.36 (d, J = 12.4 Hz, 1H),
7.19 (d, J = 6.4 Hz, 1H), 7.34-7.42 (m, 2H), 8.00 (d, J = 12.4 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 14.4,
21.4, 27.0, 60.7, 120.7, 127.8, 127.8, 130.6, 132.9, 134.5, 140.5, 142.3, 166.7, 169.5; HRMS (ESI): m/z
calculated for C14H17NNaO3 [M+Na]+: 270.1101, found: 270.1092
+
(E)-ethyl 3-(5-methoxy-2-(methylcarbamoyl)phenyl)acrylate (4c):
a
colorless solid; IR (KBr) ν 2985, 2942, 1715, 16641, 1625, 1546, 1314, 1293,
1228, 1182, 1034, 974, 862 cm-1; 1H NMR (CDCl3, 400 MHz) δ 1.32 (t, J = 7.3
Hz , 3 H), 2.98 (d, J = 5.0 Hz, 3H), 3.83 (s, 3H), 4.24 (q, J = 7.3 Hz, 2H), 5.88
(brs, 1H), 6.33 (d, J = 16.7 Hz, 1H), 6.89 (dd, J = 2.3, 8.7 Hz, 1H), 7.06 (d, J = 2.3 Hz, 1H), 7.43 (d, J = 8.7
Hz, 1s) 8.02 (d, J = 16.5 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 14.4, 27.1, 55.6, 60.8, 112.2, 115.4,
+
121.1, 129.5, 129.7, 135.0, 142.3, 161.0, 166.6, 169.2; HRMS (ESI): m/z calculated for C14H17NNaO4
[M+Na]+: 286.1050, found: 286.1054
(E)-ethyl 3-(5-fluoro-2-(methylcarbamoyl)phenyl)acrylate (4d): a colorless
solid; IR (KBr) ν 3082, 2984, 1721, 1635, 1558, 1321, 1182, 1034, 971, 855 cm-1;
1H NMR (CDCl3, 400 MHz) δ 1.30 (t, J = 6.8 Hz , 3 H), 2.99 (d, J = 5.0 Hz, 3H),
4.24 (q, J = 6.8 Hz, 2H), 5.95 (brs, 1H), 6.34 (d, J = 16.5 Hz, 1H), 7.04 (ddd, J =
2.8, 8.7, 8.7 Hz, 1H), 7.25 (dd, J = 2.8, 10.1 Hz, 1H), 7.44 (dd, J = 6.0, 8.7 Hz, 2H), 7.91 (d, J = 16.5 Hz,
1H); 13C NMR (CDCl3, 100 MHz) δ 14.4, 27.1, 60.9, 113.9 (d, J = 22.9 Hz), 116.8 (d, J = 22.9 Hz), 122.1,
130.6 (d, J = 9.5 Hz), 133.4 (d, J = 2.9 Hz), 135.5 (d, J = 7.6 Hz), 140.8 (d, J = 2.9 Hz), 163.5 (d, J = 254.7
Hz), 166.3, 168.6; HRMS (ESI): m/z calculated for C13H14FNNaO3 [M+Na]+: 274.0850, found: 274.0844
+
(E)-ethyl 3-(5-bromo-2-(methylcarbamoyl)phenyl)acrylate (4e): a colorless
solid; IR (KBr) ν 3079, 2975, 2935, 1719, 1642, 1561, 1316, 1190, 1032, 979,
1
862 cm-1; H NMR (CDCl3, 400 MHz) δ 1.32 (t, J = 7.5 Hz , 3 H), 3.00 (d, J =
5.2 Hz, 3H), 4.23 (q, J = 7.5 Hz, 2H), 5.88 (brs, 1H), 6.36 (d, J = 16.0 Hz, 1H),
7.34 (d, J = 8.6 Hz, 1H), 7.49 (d, J = 8.6 Hz, 1H), 7.74 (s, 1H) 7.90 (d, J = 16.0 Hz, 1H); 13C NMR (CDCl3,
S-2

ACCEPTED MANUSCRIPT
100 MHz) δ 14.4, 27.1, 60.1, 122.1, 124.1, 124.7, 129.3, 130.1, 132.7, 134.9, 135.8, 140.5, 166.2, 168.5;
HRMS (ESI): m/z calculated for C13H14BrNNaO3 [M+Na]+: 334.0049, found: 334.0050
+
(E)-ethyl 3-(2-(methylcarbamoyl)-5-(trifluoromethyl)phenyl)acrylate (4f):
a colorless solid; IR (KBr) ν 3084, 2974, 1717, 1642, 1551, 1337, 1292, 1159,
1
1122, 1042, 989, 924, 843 cm-1; H NMR (CDCl3, 400 MHz) δ 1.33 (t, J = 6.9
Hz , 3 H), 3.04 (d, J = 4.6 Hz, 3H), 4.24 (q, J = 6.9 Hz, 2H), 5.88 (brs, 1H), 6.45
(d, J = 16.0 Hz, 1H), 7.57-7.65 (m, 2H), 7.85 (s, 1H) 7.94 (d, J = 16.0 Hz, 1H); 13C NMR (CDCl3, 100
MHz) δ 14.4, 27.1, 61.0, 122.6, 123.5 (q, J = 273.4 Hz), 124.1 (q, J = 3.8 Hz), 126.3 (q, J = 22.9 Hz),
128.4, 132.5 (q, J = 32.9 Hz), 133.7; HRMS (ESI): m/z calculated for C14H14F3NNaO3 [M+Na]+: 324.0818,
+
found: 324.0818
(E)-ethyl 3-(2-(methylcarbamoyl)-5-nitrophenyl)acrylate (4g): a colorless
solid; IR (KBr) ν 3085, 2977, 1713, 1643, 1556, 1522, 1352, 1282, 1040, 989,
1
825 cm-1; H NMR (CDCl3, 400 MHz) δ 1.31 (t, J = 7.3 Hz , 3 H), 3.03 (d, J =
5.0 Hz, 3H), 4.26 (q, J = 7.3 Hz, 2H), 6.14 (brs, 1H), 6.50 (d, J = 16.5 Hz, 1H),
7.62 (d, J = 8.7 Hz, 1H), 7.89 (d, J = 16.5 Hz, 1H), 8.19 (d, J = 8.7 Hz, 1H) 8.43 (s, 1H); 13C NMR (CDCl3,
100 MHz) δ 14.4, 27.2, 61.2, 122.1, 123.7, 124.2, 134.7, 139.4, 142.3, 148.8, 165.9, 167.5; HRMS (ESI):
m/z calculated for C13H14N2NaO5 [M+Na]+: 301.0795, found: 301.0791
+
(E)-methyl 3-(3-ethoxy-3-oxoprop-1-en-1-yl)-4-(methylcarbamoyl)benzoate (4h): a colorless solid; IR
(KBr) ν 3082, 2988, 2954, 1721, 1644, 1551, 1320, 1252, 1184, 1032, 976,
866, 760 cm-1; 1H NMR (CDCl3, 400 MHz) δ 1.32 (t, J = 7.2 Hz , 3 H), 3.02
(d, J = 4.8 Hz, 3H), 3.94 (s, 3H), 4.25 (q, J = 7.2 Hz, 2H), 6.07 (brs, 1H),
6.46 (d, J = 16.0 Hz, 1H), 7.50 (d, J = 7.6 Hz, 1H), 7.92 (d, J = 16.0 Hz, 1H),
13
7.99 (d, J = 7.6 Hz, 1H), 8.35 (s, 1H); C NMR (CDCl3, 100 MHz) δ 14.4, 27.1, 52.7, 60.9, 122.1, 122.1,
127.9, 128.4, 130.6, 131.9, 133.2, 140.8, 140.9, 166.0, 166.4, 168.6; HRMS (ESI): m/z calculated for
C15H17NNaO5 [M+Na]+: 314.0999, found: 314.0993
+
(E)-ethyl 3-(4-methyl-2-(methylcarbamoyl)phenyl)acrylate (4k): a colorless
solid; IR (KBr) ν 2979, 1715, 1639, 1604, 1541, 1309, 1272, 1178, 1030, 977,
1
822 cm-1; H NMR (CDCl3, 400 MHz) δ 1.30 (t, J = 7.3 Hz , 3 H), 2.35 (s, 3H),
3.00 (d, J = 5.0 Hz, 3H), 4.22 (q, J = 7.3 Hz, 2H), 5.88 (brs, 1H), 6.32 (d, J =
16.0 Hz, 1H), 7.29-7.37 (m, 2H), 7.48 (d, J = 8.2 Hz, 1H), 7.92 (d, J = 16.0 Hz, 1H); 13C NMR (CDCl3, 100
S-3

ACCEPTED MANUSCRIPT
MHz) δ 14.4, 21.4, 27.0, 60.7, 119.9, 127.2, 128.4, 129.9, 131.1, 137.3, 140.4, 141.8, 166.8, 169.6; HRMS
(ESI): m/z calculated for C14H17NNaO3 [M+Na]+: 270.1101, found: 270.1104
+
(E)-ethyl 3-(4-bromo-2-(tert-butylcarbamoyl)phenyl)acrylate (4l):
a
colorless oil; IR (neat) ν 3065, 2973, 1714, 1641, 1541, 1312, 1263, 1178, 1097,
1
1041, 976, 895, 816 cm-1; H NMR (CDCl3, 400 MHz) δ 1.31 (t, J = 7.3 Hz , 3
H), 1.47(s, 9H), 4.24 (q, J = 7.3 Hz, 2H), 5.64 (brs, 1H), 6.35 (d, J = 16.5 Hz,
1H), 7.43 (d, J = 7.8 Hz, 1H), 7.52 (dd, J = 2.3, 7.8 Hz, 1H), 7.57 (s, J = 2.3 Hz, 1H), 7.85 (d, J = 16.5 Hz,
1H); 13C NMR (CDCl3, 100 MHz) δ 14.4, 28.8, 52.7, 60.8, 121.3,124.0, 128.5, 130.7, 131.2, 133.1, 140.0,
140.7, 166.3, 166.7; HRMS (ESI): m/z calculated for C16H21NNaO3 [M+Na]+: 376.0519, found: 376.0520
+
(E)-ethyl 3-(3-methyl-2-(methylcarbamoyl)phenyl)acrylate (4m): a colorless oil;
1
IR (neat) ν 2980, 1710, 1638, 1543, 1313, 1233, 1090, 1039, 979, 867, 790 cm-1; H
NMR (CDCl3, 400 MHz) δ 1.31 (t, J = 7.3 Hz , 3 H), 2.34 (s, 3H), 3.04 (d, J = 5.0 Hz,
3H), 4.22 (q, J = 7.3 Hz, 2H), 5.72 (brs, 1H), 6.38 (d, J = 16.0 Hz, 1H), 7.21 (d, J =
7.8 Hz, 1H), 7.28 (dd, J = 7.8, 7.8 Hz, 1H), 7.70 (d, J = 16.0 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 14.4,
19.3, 26.8, 60.7, 120.8, 124.0, 1293, 131.7, 121.9, 135.6, 138.2, 141.6, 166.7, 169.8; HRMS (ESI): m/z
calculated for C14H17NNaO3 [M+Na]+: 270.1101, found: 270.1102
+
(E)-ethyl 3-(3-(methylcarbamoyl)naphthalen-2-yl)acrylate (4n): a colorless
solid; IR (KBr) ν 2981, 1715, 1644, 1622, 1551, 1304, 1177, 1033, 976, 863,
1
758 cm-1; H NMR (CDCl3, 400 MHz) δ 1.33 (t, J = 7.3 Hz , 3 H), 3.05 (d, J =
5.0 Hz, 3H), 4.26 (q, J = 7.3 Hz, 2H), 6.14 (brs, 1H), 6.44 (d, J = 16.5 Hz, 1H),
7.50-7.57 (m, 2H), 7.76-7.87 (m, 2H), 7.91 (s, 1H), 8.01 (s, 1H), 8.23 (d, J = 16.5 Hz, 1H); 13C NMR (CDCl3,
100 MHz) δ 14.5, 27.1, 60.7, 120.8, 127.6, 127.7, 127.8, 127.9, 128.2, 128.4, 130.4, 133.0, 133.6, 134.4,
142.5, 166.7, 169.5; HRMS (ESI): m/z calculated for C17H17NNaO3 [M+Na]+: 306.1101, found: 306.1105
+
(E)-ethyl 3-(2-(tert-butylcarbamoyl)phenyl)acrylate (4o): a colorless oil; IR (neat)
1
ν 3063, 2971, 1712, 1639, 1538, 1314, 1177, 1094, 1042, 977, 879, 764 cm-1; H
NMR (CDCl3, 400 MHz) δ 1.33 (t, J = 7.3 Hz , 3 H), 1.49 (s, 9H), 4.26 (q, J = 7.3 Hz,
2H), 5.55 (brs, 1H), 6.39 (d, J = 16.0 Hz, 1H), 7.36-7.50 (m, 3H), 7.59 (s, J = 7.4 Hz,
1H), 7.98 (d, J = 16.0 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 14.4, 28.9, 52.4, 60.7, 120.8, 127.0, 127.7,
+
130.0, 130.1, 132.3, 138.7, 142.0, 166.6, 168.3; HRMS (ESI): m/z calculated for C16H20BrNNaO3
[M+Na]+: 298.1414, found: 298.1423
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(E)-ethyl 3-(2-(methylcarbamoyl)thiophen-3-yl)acrylate (4p): a colorless solid; IR
1
(neat) ν 2979, 1707, 1632, 1536, 1244, 1178, 1037, 987, 867, 774 cm-1; H NMR
(CDCl3, 400 MHz) δ 1.33 (t, J = 6.9 Hz , 3 H), 3.01 (s, 3H), 4.26 (q, J = 6.9 Hz, 2H),
6.33 (d, J = 16.5 Hz, 1H), 5.84 (brs, 1H), 7.29 (d, J = 5.5 Hz, 1H), 7.33 (d, J = 5.5 Hz,
1H), 8.26 (d, J = 16.5 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 14.5,27.2, 60.8, 121.7, 127.0, 127.2, 136.4,
136.5, 138.6, 162.8, 162.9; HRMS (ESI): m/z calculated for C11H13NNaO3S+ [M+Na]+: 262.0508, found:
262.0513
(E)-ethyl 3-(2-acetamidophenyl)acrylate: a colorless solid; IR (KBr) ν 2978, 1712,
1
1659, 1537, 1455, 1302, 1270, 1045, 971, 764, 743 cm-1; H NMR (CDCl3, 400
MHz) δ 1.33 (t, J = 7.6 Hz , 3 H), 2.23 (s, 3H), 4.26 (q, J = 7.6 Hz, 2H), 6.39 (d, J = 16.0
Hz, 1H), 7.20 (m, 1H), 7.29-7.43 (m, 2H), 7.54 (d, J = 7.6 Hz, 1H), 7.70-7.90 (m, 2H);
13C NMR (CDCl3, 100 MHz) δ 14.4, 24.4, 60.9, 120.9, 125.3, 126.0, 127.3, 127.7,
130.9, 136.0, 139.4, 166.9, 169.0; HRMS (ESI): m/z calculated for C13H15NNaO3 [M+Na]+: 256.0944,
+
found: 256.0936
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