Ligand-free PdCl2-catalyzed heck reaction of arylboronic acids and olefins under reusable TBAB/H2O conditions

Article abstract of DOI:10.1055/s-0033-1339650

A novel method was developed for Heck reaction of olefins and arylboronic acids using a ligand-free PdCl₂ catalyst to afford the coupling products with excellent regio- and stereoselectivity. It is noteworthy that the PdCl₂/CuSO₄/K₂CO₃/TBAB/H ₂O system can be recovered and used for three cycles directly. Georg Thieme Verlag Stuttgart, New York.

Full text of DOI:10.1055/s-0033-1339650

PAPER
▌2971
paper
Ligand-Free PdCl2-Catalyzed Heck Reaction of Arylboronic Acids and Olefins
under Reusable TBAB/H2O Conditions
Ligand-Free PdCl2-Catalyzed Heck Reaction of Arylboronic Acids
Bo-Xiao Tang,* Xiao-Niu Fang, Ren-Yun Kuang, Rong-Hua Hu, Ji-Wei Wang, Ping Li, Xiao-hang Li
School of Chemistry and Chemical Engineering, The Key Laboratory of Coordination Chemistry of Jiangxi Province, and Institute of Applied
Chemistry, Jinggangshan University, Ji’an, 343009, P. R. of China
Fax +86(796)8110 676; E-mail: 520tangboxiao@163.com
Received: 10.07.2013; Accepted after revision: 31.07.2013
Rh-catalyst phosphine ligand
Abstract: A novel method was developed for Heck reaction of ole-
fins and arylboronic acids using a ligand-free PdCl2 catalyst to
afford the coupling products with excellent regio- and stereoselec-
tivity. It is noteworthy that the PdCl2/CuSO4/K2CO3/TBAB/H2O
system can be recovered and used for three cycles directly.
or
SiO2-Rh(0), LDH-Rh(0)
R
(1)
+
Ar B(OH)2
Ar
R
organic solvent/H2O
Key words: ligand-free, reusability, PdCl2, Heck reaction, arylbo-
ronic acids
PhP
SO3K
P
P
2
3
phosphine ligand =
Me
+N
Me
Me
P
CO2Li
3
Transition-metal-catalyzed Heck reaction is an extremely
powerful tool for C–C bond formation and has been wide-
ly utilized in the synthesis of valuable intermediates, bio-
logically active agents, and functional organic materials.1
Among them, Heck reaction of olefins and boron reagents
has received considerable attention using various oxidant
systems.2 In recent years, Rh- and Pd-catalyzed Heck cou-
pling reactions of arylboronic acids have been particularly
attractive under organic solvent/H2O conditions.
Lautens,3 Zou,4 Michelet,5 and their co-workers reported
Rh-catalyzed Heck coupling of arylboronic acids with
olefins in the presence of phosphine ligands. Similarly,
SiO2-Rh(0)- and LDH-Rh(0)-catalyzed Heck-type reac-
tions of arylboronic acids were also reported by Trivedi et
al. using a toluene–H2O (5:1) system (Scheme 1, equation
1).6 In 2011, Minnaard and co-workers reported that
Pd(OAc)2/BIAN ligand is an excellent catalyst for the
base-free oxidative Heck reaction of arylboronic acids un-
der MeOH–H2O (9:1) conditions (Scheme 1, equation 2).7
Cl–
O
Pd(OAc)2 (5 mol%)
MeOH–H2O (9:1)
(2)
+
B(OH)2
FG
FG
O
N
N
(7 mol%)
PdCl2 (5 mol%)
R1
R1
R2
+
B(OH)2
(3)
TBAB/H2O (1:1)
ligand-free
R2
reusable
this work
Scheme 1 Rh- and Pd-catalyzed Heck coupling reactions of arylbo-
From an economical as well as environmental point of
view, it is highly desirable to design a ligand-free and
green heterogeneous system for this elegant cross-cou-
pling reaction. We have been engaged for a long time in a
program devoted to reusable ionic liquid system.8 There-
fore, we aimed to develop an efficient green solvent sys-
tem for Pd-catalyzed Heck reaction of arylboronic acids
using a reusable procedure that is simple and easy to op-
erate. Herein, we report a novel Heck-type cross-coupling
reaction of olefins and arylboronic acids using a ligand-
free palladium catalyst under reusable TBAB (n-
Bu4NBr)/H2O conditions (Scheme 1, equation 3).
ronic acids under organic solvent/H2O conditions
tyl acrylate (2a) in the presence of 5 mol% PdCl2 as a cat-
alyst under various reaction conditions (Table 1). As
shown in Table 1, a range of aqueous media including
TBAF (tetrabutylammonium fluoride)/H2O, EMIB
(1-ethyl-3-methyl imidazolium bromide)/H2O, EMPB
(1-ethyl-1-methyl piperidine bromide)/H2O, and EPB
(N-ethylpyridinium bromide)/H2O were screened; how-
ever, the yields of the target product 3a were all less than
30% (Table 1, entries 1–4). To our delight, the Heck-type
reaction exhibited high catalytic activity in the presence of
TBAB/H2O (entry 5, the product 3a is an E-alkene). Sub-
sequently, a series of oxidants were evaluated, and CuSO4
was found to provide higher yield than Cu(OAc)2, TBHP,
AgOAc, CuCl2 (entries 5–9). Using 1.5 and 2.5 equiva-
lents of CuSO4, 73% and 29% yield of 3a could be ob-
tained, respectively (entries 10, 11). Product 3a was
We began our investigation by studying the Heck-type
coupling reaction of phenylboronic acid (1a) with tert-bu-
SYNTHESIS 2013, 45, 2971–2976
Advanced online publication: 29.08.2013
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X
DOI: 10.1055/s-0033-1339650; Art ID: SS-2013-F0473-OP
© Georg Thieme Verlag Stuttgart · New York

2972
B.-X. Tang et al.
PAPER
Table 1 Screening Conditions for Heck-Type Reaction between tert-Butyl Acrylate and Phenylboronic Acida
PdCl2 (5 mol%)
O
+
O
base, oxidant
O
B(OH)2
O
1a
2a
3a
Me
+
+
N
N
N+ Et
Br–
+
N
N
+
N
Br–
Br–
F–
Br–
Et
Me Et
EMIB
EMPB
EPB
TBAB
TBAF
Entry
Oxidant
Ionic liquid/H2O
Base
Yield (%)b
1
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
TBHP
TBAF/H2O
EMIB/H2O
EMPB/H2O
EPB/H2O
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
KOAc
NaOH
Cs2CO3
–
25
2
<10
28
3
4
26
5
TBAB/H2O
TBAB/H2O
TBAB/H2O
TBAB/H2O
TBAB/H2O
TBAB/H2O
TBAB/H2O
TBAB/H2O
TBAB/H2O
TBAB/H2O
TBAB/H2O
TBAB/H2O
TBAB/H2O
TBAB/H2O
83
6c
7
19
AgOAc
CuCl2
21
8
79
9
CuSO4
90
10d
11e
12 f
13g
14h
15
16
17
18
CuSO4
73
CuSO4
29
CuSO4
69
CuSO4
73
CuSO4
76
CuSO4
<10
<10
80
CuSO4
CuSO4
CuSO4
trace
a Reaction conditions: 1a (0.6 mmol), 2a (0.4 mmol), PdCl2 (5 mol%), oxidant (2 equiv), base (2 equiv), ionic liquid (0.5 g)/H2O (0.5 g) = 1:1,
10 h, 85 °C, air.
b Isolated yield.
c TBHP = tert-butyl hydroperoxide.
d CuSO4 (1.5 equiv).
e CuSO4 (2.5 equiv).
f CuSO4 (1.5 equiv), O2.
g TBAB/H2O = 7:3.
h TBAB/H2O = 3:7.
obtained in 69% yield using 1.5 equivalents of CuSO4/O2 and Cs2CO3 (entries 9, 15–17). Only a trace amount of the
(entry 12). The ratio of TBAB and H2O were then inves- target product 3a was observed without base (entry 18).
tigated; the target product 3a could be isolated in 73% and
76% yield with a TBAB/H2O ratio of 7:3 and 3:7, respec-
tively (entries 13, 14). Finally, comparison of the different
bases indicated that K2CO3 was superior to KOAc, NaOH,
The palladium-catalyzed coupling reaction of arylboronic
acids 1 with olefins 2 were conducted under optimized
conditions, and the results are summarized in Table 2.
Various olefins with phenylboronic acid (1a) were trans-
Synthesis 2013, 45, 2971–2976
© Georg Thieme Verlag Stuttgart · New York

PAPER
Ligand-Free PdCl2-Catalyzed Heck Reaction of Arylboronic Acids
2973
Table 2 Ligand-Free PdCl2-Catalyzed Heck-Type Reaction of Aryl-
formed into the corresponding products 3 ranging from
36–81% yields (Table 2, entries 1–5). Electronic effect of
the substrates 2 seemed to have a distinction in the yields.
For example, the yields of n-hexyl acrylate (2c) (81%) and
acrylamide (2d) (66%) implied that there was discrimina-
tion between different electron-withdrawing functional
groups (entries 2, 3). Allyl phenyl ether (2e) and styrene
(2f) also affected the coupling reaction (entries 4, 5). All
the alkenes afforded the target products exclusively with
E-configuration.
boronic Acidsa (continued)
PdCl2 (5 mol%)
R1
R1
R2
+
2
TBAB/H2O (1:1)
CuSO4, K2CO3
R2
B(OH)2
1
3
Entry Arylboronic acid
Olefin
Time Product,
(h)
10
10
10
yield
(%)b
N
B(OH)2
Table 2 Ligand-Free PdCl2-Catalyzed Heck-Type Reaction of Aryl-
10
11
12
2a
3j, 79
3k, 84
3l, 65
boronic Acidsa
1f
PdCl2 (5 mol%)
R1
R1
R2
+
C3H7O
B(OH)2
2
TBAB/H2O (1:1)
CuSO4, K2CO3
R2
2a
2a
B(OH)2
1
3
1g
Entry Arylboronic acid
Olefin
Time Product,
O
(h)
yield
B(OH)2
(%)b
H
1h
O
O
O
B(OH)2
1
12
3b, 70
B(OH)2
13
14
15
2a
2a
2a
10
10
10
3m, 70
3n, 58
3o, 62
H2N
1a
2b
1i
O
C6H11
2
3
1a
1a
10
14
3c, 81
3d, 66
O
Cl
B(OH)2
2c
NH2
1j
B(OH)2
O
2d
1k
a Reaction conditions: 1 (0.6 mmol), 2 (0.4 mmol), PdCl2 (5 mol%),
CuSO4 (0.8 mmol), K2CO3 (0.8 mmol), TBAB (0.5 g)/H2O (0.5 g) =
1:1, air, 85 °C.
4
5
1a
20
12
3e, 36
3f, 62
O
2e
2f
b Isolated yield.
c Amount of 1b used: 0.2 mmol.
1a
We were also pleased to observe that the Heck-type reac-
tion of tert-butyl acrylate (2a) with various boron reagents
proceeded well to give the target products in moderate to
excellent yields under the standard conditions (Table 2,
entries 6–15). Reaction of 2,4,6-triphenyl-1,3,5,2,4,6-tri-
oxatriborinane (1b; 0.2 mmol) with 2a provided the prod-
uct in 85% yield (entry 6). A variety of arylboronic acids
1f,g, having electron-donating groups on the aromatic
ring were examined in the presence of TBAB/H2O. The
results demonstrated that several functional groups, such
as dimethylamino and propoxy groups, were tolerated
well under the standard conditions (entries 10, 11). Some
ortho-substituted phenylboronic acids were also exam-
ined, and less amount of product was obtained in view of
steric hindrance effect (entries 7, 8). Reactions with elec-
tron-deficient phenylboronic acids 1h, 1i, and 1j also pro-
ceed smoothly (entries 12–14). When naphthalen-2-
ylboronic acid (1k) was used, the desired product was ob-
tained in 62% yield (entry 15). All the coupling products
3 were in the E-isomeric form.
Ph
O
Ph
B
B
O
O
O
6c
10
10
10
10
3a, 85
3g, 79
3h, 69
3i, 76
B
O
Ph
2a
2a
1b
1c
7
B(OH)2
B(OH)2
8
2a
2a
1d
B(OH)2
9
F
1e
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 2971–2976

2974
B.-X. Tang et al.
PAPER
as monitored by TLC (hexane–EtOAc, 30:1). After completion of
the reaction, the mixture was cooled to r.t., diluted with Et2O (15
mL), washed with sat. NaCl solution (2 × 5 mL), dried over anhy-
drous Na2SO4 (2 g), and transferred to a round-bottom flask. The or-
ganic extract was concentrated under vacuum, and the resulting
residue was purified by silica gel column chromatography (hexane–
EtOAc) to afford the desired product 3a; yield: 73.2 mg (90%); col-
orless oil.
Next the reusability of PdCl2/CuSO4/K2CO3/TBAB/H2O
system in the Heck-type reaction of 1a and 2a was studied
(Table 3). After initial coupling experimentation, the reac-
tion mixture was extracted with hexane–ethyl acetate, and
the PdCl2/CuSO4/K2CO3/TBAB/H2O system was then
evaporated under vacuum and cooled. The recovered
Heck-type reaction system was employed in the next run
by charging with 1a and 2a. The results of three runs
showed that the yield of the target product 3a decreased
significantly after each cycle (run 1, 89%; run 2, 72%; run
3, 61%).
IR (film): 1708, 1638, 1329, 1151 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.61 (d, J = 16.0 Hz, 1 H), 7.52–
7.48 (m, 2 H), 7.38–7.34 (m, 3 H), 6.40 (d, J = 16.0 Hz, 1 H), 1.54
(s, 9 H).
13C NMR (100 MHz, CDCl3): δ = 166.3, 143.5, 134.5, 129.9, 128.7,
127.9, 120.0, 80.4, 28.1.
Table 3 Reusability of PdCl2/CuSO4/K2CO3/TBAB/H2O System in
the Heck-Type Reaction of Phenylboronic Acid (1a) with tert-Butyl
Acrylate (2a)
LRMS (EI, 70 eV): m/z (%) = 204 (M+, 15), 147 (M+ – t-Bu, 100).
Ethyl (E)-Cinnamate (3b)9a
Yield: 49.3 mg (70%); colorless oil.
IR (film): 1713, 1638, 1311, 1177 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.71 (d, J = 16.0 Hz, 1 H), 7.54–
7.51 (m, 2 H), 7.39–7.36 (m, 3 H), 6.46 (d, J = 16.0 Hz, 1 H), 4.29
(q, J = 7.2 Hz, 2 H), 1.36 (t, J = 7.2 Hz, 3 H).
B(OH)2
1a
PdCl2 (5 mol%)
O
+
TBAB/H2O (1:1)
CuSO4, K2CO3
O
O
3a
13C NMR (100 MHz, CDCl3): δ = 166.8, 144.5, 134.3, 130.2, 128.8,
128.0, 118.1, 60.5, 14.3.
O
2a
LRMS (EI, 70 eV): m/z (%) = 176 (M+, 33), 131 (M+ – OC2H5, 100).
Olefin Arylboronic acid Cycle Time (h) Yield (%)a of 3a
1b
2c
3c
10
13
16
89
72
61
Hexyl (E)-Cinnamate (3c)
Yield: 75.1 mg (81%); colorless oil.
IR (film): 1714, 1638, 1310, 1170 cm–1.
1a
2a
1H NMR (400 MHz, CDCl3): δ = 7.71 (d, J = 16.0 Hz, 1 H), 7.54–
7.52 (m, 2 H), 7.39–7.37 (m, 3 H), 6.47 (d, J = 16.0 Hz, 1 H), 4.22
(t, J = 7.2 Hz, 2 H), 1.74–1.67 (m, 2 H), 1.42–1.31 (m, 6 H), 0.92–
0.89 (m, 3 H).
a Isolated yield.
b Reaction conditions: 1a (0.6 mmol), 2a (0.4 mmol), PdCl2 (5 mol%),
CuSO4 (0.8 mmol), K2CO3 (0.8 mmol), TBAB (0.5 g)/H2O (0.5 g) =
1:1, air, 85 °C.
c Amounts present: 1a (0.6 mmol), 2a (0.4 mmol).
13C NMR (100 MHz, CDCl3): δ = 167.1, 144.5, 134.3, 130.2, 128.8,
128.0, 118.1, 64.7, 31.4, 28.6, 25.6, 22.5, 14.0.
LRMS (EI, 70 eV): m/z (%) = 232 (M+, 3), 131 (M+ – OC6H13, 25),
117 (100).
In summary, we have developed a novel ligand-free
PdCl2-catalyzed method for Heck-type coupling of aryl-
boronic acids under TBAB/H2O conditions. The scope of
the catalytic system is well documented in the Heck-type
reaction of various arylboronic acids and alkenes to afford the
coupling products with excellent regio- and stereoselectivity.
It is noteworthy that the PdCl2/CuSO4/K2CO3/TBAB/H2O
system can be recovered and used for three cycles direct-
ly. Studies to broaden the scope of the catalytic system are
currently underway.
(E)-Cinnamamide (3d)2b
Yield: 38.6 mg (66%); pale yellow solid; mp 132–133 °C.
IR (KBr): 3375, 3173, 1662, 1608, 1399 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.68 (d, J = 15.6 Hz, 1 H), 7.54–
7.51 (m, 2 H), 7.39–7.38 (m, 3 H), 6.50 (d, J = 15.6 Hz, 1 H), 5.85
(br, 2 H).
13C NMR (100 MHz, CDCl3): δ = 167.8, 142.5, 134.4, 130.0, 128.8,
127.9, 119.3.
LRMS (EI, 70 eV): m/z (%) = 147 (M+, 46), 146 (M+ – H, 100), 131
(M+ – NH2, 48).
Starting materials and other reagents were obtained from commer-
1
cial suppliers and used without further purification. H and 13C
(E)-1-(3-Phenoxyprop-1-enyl)benzene (3e)9b
Yield: 30.2 mg (36%); white solid; mp 61–62 °C.
IR (KBr): 3436, 1593, 1495, 1238 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.42 (d, J = 7.6 Hz, 2 H), 7.34–
7.21 (m, 5 H), 6.97 (d, J = 8.4 Hz, 3 H), 6.74 (d, J = 16.0 Hz, 1 H),
6.45–6.40 (m, 1 H), 4.69 (d, J = 5.6 Hz, 2 H).
13C NMR (100 MHz, CDCl3): δ = 158.5, 136.4, 132.9, 129.5, 128.5,
127.8, 126.5, 124.4, 120.8, 114.7, 68.4.
NMR spectra were recorded at 400 and 100 MHz on a Bruker
ARX400 spectrometer. Melting points were recorded in capillary
tubes heated slowly in paraffin oil and are uncorrected. IR and
LRMS data were recorded on a Thermo Nicolet AVATAR 370 and
a Shimadzu GCMS-QP2010, respectively.
Heck-Type Reaction; tert-Butyl (E)-3-Phenylpropenoate (3a);9a
Typical Procedure
To a Schlenk tube were added phenylboronic acid (1a; 73.2 mg, 0.6
mmol), tert-butyl acrylate (2a; 51.2 mg, 0.4 mmol), PdCl2 (3.6 mg,
5 mol%), CuSO4 (127.1 mg, 0.8 mmol), K2CO3 (110.4 mg, 0.8
mmol), TBAB (0.5 g), and H2O (0.5 g). Then, the tube was charged
with air, and the reaction mixture was stirred at 85 °C (oil bath
temp) for 10 h until complete consumption of the starting material
LRMS (EI, 70 eV): m/z (%) = 210 (M+, 5), 117 (M+ – OC6H5, 100).
(E)-1,2-Diphenylethene (3f)9a
Yield: 44.5 mg (62%); white solid; mp 122–123 °C.
Synthesis 2013, 45, 2971–2976
© Georg Thieme Verlag Stuttgart · New York

PAPER
Ligand-Free PdCl2-Catalyzed Heck Reaction of Arylboronic Acids
2975
IR (KBr): 3445, 1384, 765, 693 cm–1.
tert-Butyl (E)-3-(4-Formylphenyl)acrylate (3l)
Yield: 60.3 mg (65%); pale yellow solid; mp 100–102 °C.
IR (KBr): 2717, 1703, 1638, 1151 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.51 (d, J = 7.6 Hz, 4 H), 7.37 (t,
J = 7.6 Hz, 4 H), 7.27 (d, J = 7.2 Hz, 2 H), 7.10 (s, 2 H).
13C NMR (100 MHz, CDCl3): δ = 137.2, 128.6, 128.5, 127.6, 126.5.
LRMS (EI, 70 eV): m/z (%) = 180 (M+, 100).
1H NMR (400 MHz, CDCl3): δ = 10.03 (s, 1 H), 7.90 (d, J = 8.4 Hz,
2 H), 7.67 (d, J = 8.4 Hz, 2 H), 7.63 (d, J = 16.0 Hz, 1 H), 6.51 (d,
J = 16.0 Hz, 1 H), 1.55 (s, 9 H).
tert-Butyl (E)-3-(3,4-Dimethylphenyl)acrylate (3g)
Yield: 73.3 mg (79%); colorless oil.
13C NMR (100 MHz, CDCl3): δ = 191.5, 165.7, 141.8, 140.4, 136.9,
130.1, 128.3, 123.4, 81.0, 28.1.
LRMS (EI, 70 eV): m/z (%) = 232 (M+, 8), 176 (100).
IR (film): 1705, 1635, 1322, 1151 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.56 (d, J = 16.0 Hz, 1 H), 7.28 (s,
1 H), 7.26 (d, J = 7.6 Hz, 1 H), 7.13 (d, J = 7.6 Hz, 1 H), 6.35 (d, J =
16.0 Hz, 1 H), 2.26 (s, 6 H), 1.53 (m, 9 H).
13C NMR (100 MHz, CDCl3): δ = 166.6, 143.7, 139.0, 137.0, 132.2,
130.0, 129.1, 125.5, 118.7, 80.2, 28.1, 19.8, 19.7.
tert-Butyl (E)-3-(4-Carbamoylphenyl)acrylate (3m)
Yield: 69.2 mg (70%); pale yellow solid; mp 196–198 °C.
IR (KBr): 1679, 1621, 1387, 1157 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.84 (d, J = 8.4 Hz, 2 H), 7.61–
7.54 (m, 3 H), 6.46 (d, J = 16.0 Hz, 1 H), 6.23 (br, 2 H), 1.54 (s, 9 H).
LRMS (EI, 70 eV): m/z (%) = 232 (M+, 19), 176 (100).
13C NMR (100 MHz, CDCl3): δ = 168.7, 166.8, 142.0, 138.1, 128.6,
tert-Butyl (E)-3-(2,3-Dimethylphenyl)acrylate (3h)
128.1, 127.9, 122.3, 80.9, 28.1.
Yield: 64.1 mg (69%); colorless oil.
IR (film): 1710, 1632, 1317, 1152 cm–1.
LRMS (EI, 70 eV): m/z (%) = 247 (M+, 8), 175 (100).
tert-Butyl (E)-3-(3-Chlorophenyl)acrylate (3n)
Yield: 55.3 mg (58%); colorless oil.
IR (film): 1709, 1639, 1319, 1152 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.92 (d, J = 15.6 Hz, 1 H), 7.31 (d,
J = 7.6 Hz, 1 H), 7.09 (d, J = 7.6 Hz, 1 H), 7.03 (t, J = 7.6 Hz, 1 H),
6.19 (d, J = 15.6 Hz, 1 H), 2.23 (s, 3 H), 2.22 (s, 3 H), 1.46 (m, 9 H).
13C NMR (100 MHz, CDCl3): δ = 166.5, 142.2, 137.2, 135.9, 133.8,
131.2, 125.6, 124.3, 121.4, 80.4, 28.1, 20.6, 15.3.
1H NMR (400 MHz, CDCl3): δ = 7.53 (d, J = 16.0 Hz, 1 H), 7.83 (s,
1 H), 7.38–7.27 (m, 3 H), 6.39 (d, J = 16.0 Hz, 1 H), 1.53 (m, 9 H).
LRMS (EI, 70 eV): m/z (%) = 232 (M+, 23), 176 (100).
13C NMR (100 MHz, CDCl3): δ = 165.9, 141.9, 136.5, 134.8, 130.1,
129.9, 127.7, 126.2, 121.6, 80.8, 28.2.
tert-Butyl (E)-3-(3-Fluoro-4-methylphenyl)acrylate (3i)
Yield: 71.8 mg (76%); colorless oil.
IR (film): 1708, 1639, 1324, 1150 cm–1.
LRMS (EI, 70 eV): m/z (%) = 238 (M+, 9), 240 (M+ + 2, 3), 182
(M+ – t-Bu, 100).
tert-Butyl (E)-3-(Naphthalen-2-yl)acrylate (3o)
Yield: 63.2 mg (62%); pale yellow solid; mp 61–63 °C.
IR (KBr): 1706, 1636, 1366, 1145 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.53 (d, J = 16.0 Hz, 1 H), 7.35–
7.31 (m, 2 H), 7.02 (t, J = 8.8 Hz, 1 H), 6.30 (d, J = 16.0 Hz, 1 H),
2.28 (s, 3 H), 1.53 (m, 9 H).
13C NMR (100 MHz, CDCl3): δ = 166.3, 163.5 (d, J = 247.9 Hz),
142.5, 131.1 (d, J = 5.6 Hz), 130.5 (d, J = 3.6 Hz), 127.2 (d, J = 8.6
Hz), 125.5 (d, J = 17.9 Hz), 119.5 (d, J = 2.2 Hz), 115.6 (d, J = 22.9
Hz), 80.4, 28.1, 14.5 (d, J = 3.5 Hz).
1H NMR (400 MHz, CDCl3): δ = 7.80 (d, J = 19.2 Hz, 1 H), 7.74–
7.68 (m, 3 H), 7.64 (s, 1 H), 7.57–7.54 (m, 1 H), 7.42–7.15 (m, 2 H),
6.42 (d, J = 16.0 Hz, 1 H), 1.47 (s, 9 H).
13C NMR (100 MHz, CDCl3): δ = 166.5, 143.7, 134.1, 133.3, 132.1,
129.7, 128.6, 128.5, 127.8, 127.1, 126.7, 123.6, 120.3, 80.6, 28.3.
LRMS (EI, 70 eV): m/z (%) = 236 (M+, 14), 180 (M+ – t-Bu, 100).
LRMS (EI, 70 eV): m/z (%) = 254 (M+, 23), 182 (100).
tert-Butyl (E)-3-[4-(Dimethylamino)phenyl]acrylate(3j)2b
Yield: 78.1 mg (79%); pale yellow solid; mp 80–82 °C.
IR (KBr): 1697, 1600, 1530, 1141 cm–1.
Acknowledgment
1H NMR (400 MHz, CDCl3): δ = 7.55 (d, J = 16.0 Hz, 1 H), 7.41 (d,
J = 8.8 Hz, 2 H), 6.65 (d, J = 8.8 Hz, 2 H), 6.18 (d, J = 16.0 Hz, 1
H), 2.99 (s, 6 H), 1.53 (s, 9 H).
This research was supported by the Education Department Founda-
tion of the Jiangxi Province (No. GJJ12471), the Doctoral Program
of Jinggangshan University (No. JZ10042), and the Natural Science
Foundation of Jiangxi Province (No. 20114BAB203028).
13C NMR (100 MHz, CDCl3): δ = 167.2, 151.4, 144.0, 129.5, 122.2,
114.3, 111.6, 79.7, 40.1, 28.2.
LRMS (EI, 70 eV): m/z (%) = 247 (M+, 35), 191 (M+ – t-Bu, 100).
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synthesis.SnoIufproi
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tgioSrantnugIifoop
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tert-Butyl (E)-3-(4-Propoxyphenyl)acrylate (3k)
Yield: 87.8 mg (84%); pale yellow solid; mp 62–64 °C.
IR (KBr): 1701, 1604, 1250, 1151 cm–1.
References
1H NMR (400 MHz, CDCl3): δ = 7.56 (d, J = 16.0 Hz, 1 H), 7.46 (d,
J = 8.8 Hz, 2 H), 6.89 (d, J = 8.8 Hz, 2 H), 6.26 (d, J = 16.0 Hz, 1
H), 3.96–3.91 (m, 2 H), 1.85–1.77 (m, 2 H), 1.53 (s, 9 H), 1.07–1.02
(s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 166.7, 160.6, 143.3, 129.5, 127.6,
117.3, 114.6, 80.1, 69.5, 28.2, 22.4, 10.5.
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© Georg Thieme Verlag Stuttgart · New York