Copper(II)-catalyzed esterification of arenecarboxylic acids with aryl- and vinyl-substituted trimethoxysilanes

Article abstract of DOI:10.1055/s-0029-1218759

In this paper, the copper(II)-catalyzed esterification reaction of arenecarboxylic acids with aryl- or vinyl-substituted trimethoxysilanes is described. A series of aryltrimethoxysilanes and arenecarboxylic acids worked well under this procedure, affording aryl benzoate derivatives in moderate to good yields. Notably, trimethoxy(vinyl)silanes also worked well under this procedure giving a facile and versatile method to access vinyl benzoate derivatives. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-0029-1218759

PAPER
2005
Copper(II)-Catalyzed Esterification of Arenecarboxylic Acids with Aryl- and
Vinyl-Substituted Trimethoxysilanes
Esterification
a
n
boxylic
A
cid
g
s
with Trimethoxy
L
silanes uo,a Changduo Pan,b Pengcheng Qian,a Jiang Cheng*a
a
College of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325000, P. R. of China
Fax +86(577)56998939; E-mail: jiangcheng@wzu.edu.cn
b
Wenzhou Institute of Industry & Science, Wenzhou 325000, P. R. of China
Received 24 February 2010; revised 16 March 2010
Table 1 Effects of Copper Sources, Solvents, and Fluoride Sources
on Formation of Phenyl Benzoate (3aa)
Abstract: In this paper, the copper(II)-catalyzed esterification reac-
tion of arenecarboxylic acids with aryl- or vinyl-substituted tri-
methoxysilanes is described. A series of aryltrimethoxysilanes and
arenecarboxylic acids worked well under this procedure, affording
aryl benzoate derivatives in moderate to good yields. Notably, tri-
methoxy(vinyl)silanes also worked well under this procedure giv-
ing a facile and versatile method to access vinyl benzoate
derivatives.
O
O
copper source (20 mol%)
additive, solvent
Ph
PhSi(OMe)3
Ph
O
Ph
OH
1a
3aa
2a
Entry
1
Cu source
F source
Solvent
Yielda (%)
10
Key words: copper(II) catalyzed, trimethoxysilanes, carboxylic
acids, esters, silver(I) fluoride
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
CuF2
TBAF·3 H2O toluene
2
KF
toluene
toluene
toluene
toluene
toluene
DMF
<5
3
CsF
FeF3
CuF2
AgF
AgF
AgF
AgF
AgF
AgF
AgF
AgF
AgF
AgF
AgF
AgF
AgF
AgF
–
<5
Benzoate derivatives are important building blocks in the
synthesis of natural and pharmacological compounds.1
The direct esterification of benzoic acid and phenol2 as
well as transesterification reactions3 are often conducted
under strongly acidic or basic conditions, which might
limit the scope of functional groups and cause side reac-
tions, such as carbonization, oxidation, etc.4 The Baeyer–
Villiger oxidation5 reaction may suffer from low regiose-
lectivity. In the past few years, the synthesis of alkyl ben-
zoate derivatives starting from aldehydes and ketones has
been developed.6,7 However, less attention has been paid
to the synthesis of aryl benzoate derivatives. Thus, from a
synthetic point of view, it is a highly desirable goal to de-
velop a versatile approach for the synthesis of aryl ben-
zoate derivatives in a simple way.
4
<5
5
30
6
65
7
<5
8
DMSO
NMP
<5
9
<5
10
11
12
13
14
15
16
17
18
19
20
21
DCE
30b
31b
72 (80)c
50
MeCN
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
CuSO4
The Chan–Lam coupling reaction, which allows aryl car-
bon–heteroatom bond formation via the oxidative cou-
pling of arylboronic acids, stannanes, or siloxanes with
N–H8,9f or O–H9 containing compounds, has been widely
studied in the last few years. Trialkoxy(aryl)silanes have
been widely used as the transmetalation reagent in C–C,10
C–N,11 and C–S12 bond formation, because of their low
cost, easy availability, nontoxic byproducts, and stability
under many reaction conditions. However, to the best of
our knowledge, the scope of Chan–Lam reaction for the
formation of C–O bonds was limited to phenol and alco-
hols, and the application of both carboxylic acids, as het-
eroatom nucleophiles, and siloxanes in the Chan–Lam
reaction for the formation of the C–O bond was less wide-
ly reported.9,13 In 2006, trimethoxy(phenyl)silane was
used for the oxidative esterification of aldehydes.14 We
CuBr2
30
Cu(OTf)2
Cu(acac)2
Cu2O
32
<5
33
CuI
30
CuBr
<5
CuF2
12
–
AgF
0
a Reaction conditions: 1a (0.2 mmol), 2a (0.3 mmol), Cu source (20
mol%), additive (2 equiv), anhyd solvent (2 mL), 130 °C, under air,
24 h. Isolated yield.
b 90 °C.
c AgF (3 equiv).
SYNTHESIS 2010, No. 12, pp 2005–2010
x
x.
x
x
.
2
0
1
0
Advanced online publication: 29.04.2010
DOI: 10.1055/s-0029-1218759; Art ID: F03910SS
© Georg Thieme Verlag Stuttgart · New York

2006
F. Luo et al.
PAPER
have devoted our efforts to the application of trialkoxy(ar- formed in only 12% yield in the absence of silver(I) fluo-
yl)silanes in many reactions.10c,i–k,11a,b Herein, we report ride (Table 1, entry 20) and no desired product was detect-
the copper(II)-catalyzed esterification reaction of arene- ed without a copper source (Table 1, entry 21). Biphenyl,
carboxylic acids with aryl- or vinyl-substituted trimeth- which is often detected in transition-metal-catalyzed cou-
oxysilanes under an air atmosphere, affording aryl or pling reactions, was formed as a byproduct.
vinyl benzoate derivatives in moderate to good yields.
With the optimized conditions in hand (Table 1, entry 12),
Initial studies were performed using benzoic acid (1a) we then explored the scope of this method. As expected, a
with trimethoxy(phenyl)silane (2a) as model substrates, series of aryltrimethoxysilanes 2a–e worked well under
employing copper(II) acetate as the catalyst at 130 °C in a these reaction conditions. Electron-donating as well as
sealed tube (Table 1). Considering that C–Si bonds gener- electron-neutral aryltrimethoxysilanes 2a–e coupled ef-
ally needs a fluoride source to activate it, we first focused fciently with benzoic acid (1a), and good yields of the
screening for the fluoride source (2 equiv) and found that products 3aa–ae were obtained (Table 2, entries 1–5).
silver(I) fluoride showed good activity (Table 1, entry 6). Steric hindrance on the aryltrimethoxysilane or the acid
The copper source used had a dramatic effect. Among the has no obvious effect on the reaction (Table 2, entries 2,
copper sources used, copper(II) fluoride exhibited the 3, 6–8). For example, 3ab, 3ca, 3fa, and 3ha were isolated
highest catalytic reactivity and 3aa was isolated in 72% in 83%, 90%, 84%, and 81% yields, respectively. This
yield (Table 1, entry 12). The yield of 3aa improved to procedure tolerated a series of functional groups, such as
80% using three equivalents of silver fluoride (Table 1, OMe, Cl, Br, and NO2 groups. Particularly, halogen-
entry 12). A profound solvent effect was also observed substituted carboxylic acids 1g–i worked well with tri-
and toluene was found to be superior. In addition, 3aa was methoxy(phenyl)silane (2a) (Table 2, entries 11–14) and
Table 2 Copper(II)-Catalyzed Esterification Reaction of Arenecarboxylic Acids with Aryltrimethoxysilanesa
O
CuF2
Ar2Si(OMe)3
Ar1COOH
+
Ar1
AgF, toluene
O
Ar2
1
Entry
1
2
3
Substrate 1
Ar1
Substrate 2
Ar2
Product
3aa
3ab
3ac
3ad
3ae
3ba
3ca
3da
3ea
3fa
Yieldb (%)
1a
1a
1a
1a
1a
1b
1c
1d
1e
1f
Ph
2a
2b
2c
2d
2e
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2e
Ph
80 (73)c (62)d
2
Ph
4-MeC6H4
83
81
65
70
82
90
81
83
84
79
81
76
60
70
45
36
3
Ph
2-MeC6H4
4
Ph
3,5-Me2C6H3
5
Ph
1-naphthyl
6
4-MeC6H4
2-MeC6H4
3-MeC6H4
4-MeOC6H4
2-MeOC6H4
4-ClC6H4
2-ClC6H4
3-ClC6H4
4-BrC6H4
3-O2NC6H4
CH=CHPh
Bn
Ph
7
Ph
8
Ph
9
Ph
10
11
12
13
14
15
16
17
Ph
1g
1h
1i
Ph
3ga
3ha
3ia
Ph
Ph
1j
Ph
3ja
1k
1l
Ph
3ka
3la
Ph
1m
1-naphthyl
3me
a Reaction conditions: Ar1CO2H 1 (0.2 mmol), Ar2Si(OMe)3 2 (0.3 mmol), CuF2 (20 mol%), AgF (3 equiv), anhyd toluene (2 mL), 130 °C, 24 h.
b Isolated yield.
c Scale increased to 0.5 mmol.
d Scale increased to 1.0 mmol.
Synthesis 2010, No. 12, 2005–2010 © Thieme Stuttgart · New York

PAPER
Esterification of Arenecarboxylic Acids with Trimethoxysilanes
2007
the remaining halogen atom could be valuable for further
manipulation. It is worth noting that cinnamic acid (1l)
was subjected to the standard procedure and phenyl cin-
namate (3la) was obtained in moderate yield (Table 2, en-
try 16). Under the optimized reaction conditions, the
reaction conducted on 0.5-mmol and 1-mmol scales
formed the product 3aa in 73% and 62% yields, respec-
tively (Table 2, entry 1). Disappointingly, aliphatic acids
did not react efficiently with aryltrimethoxysilanes. For
example, 1l and 1m provided the product 3la and 3me in
only 45% and 36% yields, respectively, and only a trace
of the desired product was detected using acetic acid as
the substrate. Importantly, the method obviated the use of
an acyl chloride and phenol in the synthesis of benzoate
derivatives. Thus, it represents an exceedingly practical
and alternative method to access aryl benzoate deriva-
tives.
Table 3 Copper(II)-Catalyzed Esterification Reaction of Arenecar-
boxylic Acids with Trimethoxy(vinyl)silanea
O
CuF2
ArCOOH
+
Si(OMe)3
Ar
O
AgF, toluene
1
2f
3
Entry Substrate 1
Product 3
Yieldb
(%)
O
COOH
1
70
O
1b
3bf
O
O
2
62
64
COOH
1c
3cf
O
O
Having demonstrated the utility of the optimized condi-
tions on aryltrimethoxysilanes, we chose trimethoxy(vi-
nyl)silane (2f) as the reaction partner. Fortunately, it ran
smoothly and vinyl esters were obtained in moderate
yields (Table 3). The direct addition of carboxylic acids to
terminal alkynes catalyzed by Hg,15 Ru,16 or Ir17 is a
straightforward and atom-economical process for the syn-
thesis of enol esters. However, the use of toxic mercury
salts or expensive catalysts greatly diminished the scope
of the aforementioned procedure. Thus, our procedure
represents a practically alternative method to access vinyl
esters.
MeO
COOH
MeO
3ef
3
4
1e
O
O
OMe
COOH
63
OMe
3ff
1f
O2N
O2N
O
O
5
6
7
67
40
68
COOH
1k
3kf
The stoichiometric reaction of trimethoxy(phenyl)silane
(2a) with copper(II) benzoate was conducted and phenyl
benzoate (3aa) was isolated in 60% yield (Scheme 1). A
working mechanism was proposed as outlined in
Scheme 2. In step (i), the reaction of copper(II) acetate
with benzoic acid forms copper(II) benzoate A. In step
(ii), phenyl is transferred to the Cu(II) center from
[RSiF(OMe)3]– B, which derives from the coordination of
aryltrimethoxysilane 2 with F–, producing intermediate
C.18 Finally, reductive elimination of intermediate C takes
place to afford the target product 3 and generate the Cu(0)
species, which is oxidized to a Cu(II) species by Ag(I).19
It should be noted that a mechanism involving Cu(III)
could not be completely excluded.20
O
COOH
Ph
Ph
O
1l
3lf
O
O
COOH
Ph
Ph
1m
3mf
a Reaction conditions: ArCO2H 1 (0.2 mmol), trimethoxy(vinyl)silane
(2f, 0.3 mmol), CuF2 (20 mol%), AgF (3 equiv), anhyd toluene (2
mL), 130 °C, 24 h.
b Isolated yield.
1H and 13C NMR spectra were measured on a 300 or 500 MHz Bruker
spectrometer (1H 300 MHz, 13C 75 or 125 MHz), in CDCl3 with
TMS as the internal standard at r.t. Column chromatography was
performed using EM Silica gel 60 (300–400 mesh).
O
O
O
AgF
Ph
Ph
O
PhSi(OMe)3
Cu
Ph
O
toluene, 130 °C
O
Ph
60%
Arenecarboxylic Acid Esters 3; General Procedure
Under air, a sealed tube was charged with carboxylic acid 1 (0.2,
0.5, or 1.0 mmol), trimethoxysilane 2 (1.5 equiv), CuF2 (20 mol%),
AgF (3 equiv), and anhyd toluene (2, 3, or 5 mL). The mixture was
stirred at 130 °C. The mixture was refluxed for 24 h, the solvent was
evaporated under reduced pressure, and the residue was purified by
flash column chromatography (silica gel) to give the product.
Scheme 1 Stoichiometric reactions of copper(II) benzoate with tri-
methoxy(phenyl)silane
In conclusion, we have developed a novel esterification
reaction of carboxylic acids with the facile prepared aryl-
and vinyl-substituted trimethoxysilanes. The procedure
obviates the use of acyl chloride and phenol, which repre-
sents a practically alternative method for the synthesis of
aryl and vinyl benzoate derivatives.
Phenyl Benzoate (3aa)21
1H NMR (300 MHz, CDCl3): d = 8.22 (d, J = 7.2 Hz, 2 H), 7.67–
7.62 (m, 1 H), 7.54–7.41 (m, 4 H), 7.31–7.21 (m, 3 H).
Synthesis 2010, No. 12, 2005–2010 © Thieme Stuttgart · New York

2008
F. Luo et al.
PAPER
Phenyl 2-Methylbenzoate (3ca)26
O
1H NMR (300 MHz, CDCl3): d = 8.18 (d, J = 7.9 Hz, 1 H), 7.52–
Ar
OH
7.42 (m, 3 H), 7.36–7.28 (m, 3 H), 7.24–7.21 (m, 2 H), 2.69 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 165.8, 150.9, 141.3, 132.7, 131.9,
131.1, 129.5, 128.6, 125.9, 125.8, 121.8, 21.9.
1
(i)
RSi(OMe)3 + F–
O
O
Cu
2
Cu(II)
Phenyl 3-Methylbenzoate (3da)27
Ar
O
O
Ar
1H NMR (300 MHz, CDCl3): d = 8.02 (d, J = 7.2 Hz, 2 H), 7.47–
7.38 (m, 4 H), 7.30–7.20 (m, 3 H), 2.45 (s, 3 H).
A
[RSiF(OMe)3]–
B
13C NMR (75 MHz, CDCl3): d = 165.3, 150.9, 138.4, 134.3, 130.6,
129.4, 128.4, 128.2, 127.3, 125.8, 121.7, 21.3.
(ii)
Ag+
(iv)
Phenyl 4-Methoxybenzoate (3ea)6a
O
1H NMR (300 MHz, CDCl3): d = 8.17 (d, J = 8.8 Hz, 2 H), 7.45–
7.40 (m, 2 H), 7.29–7.19 (m, 3 H), 6.99 (d, J = 8.8 Hz, 2 H), 3.89 (s,
3 H).
Cu
R
Ar
O
C
(iii)
13C NMR (75 MHz, CDCl3): d = 164.9, 163.9, 151.1, 132.3, 129.4,
125.7, 121.9, 121.8, 113.8, 55.5.
Cu(0)
O
Phenyl 2-Methoxybenzoate (3fa)28
R
1H NMR (300 MHz, CDCl3): d = 8.03 (d, J = 7.6 Hz, 1 H), 7.58–
7.53 (m, 1 H), 7.45–7.40 (m, 2 H), 7.28–7.22 (m, 3 H), 7.08–7.03
(m, 2 H), 3.94 (s, 3 H).
Ar
O
3
Scheme 2 Possible mechanism
13C NMR (75 MHz, CDCl3): d = 164.4, 159.9, 150.9, 134.3, 132.2,
129.3, 125.7, 121.8, 120.2, 119.1, 112.2, 56.0.
13C NMR (75 MHz, CDCl3): d = 165.2, 150.9, 133.6, 130.1, 129.6,
129.5, 128.5, 125.8, 121.7.
Phenyl 4-Chlorobenzoate (3ga)29
1H NMR (300 MHz, CDCl3): d = 8.15 (d, J = 8.6 Hz, 2 H), 7.51–
7.41 (m, 4 H), 7.31–7.20 (m, 3 H).
o-Tolyl Benzoate (3ab)22
1H NMR (300 MHz, CDCl3): d = 8.23 (d, J = 7.8 Hz, 2 H), 7.65–
7.63 (m, 1 H), 7.55–7.50 (m, 2 H), 7.30–7.25 (m, 2 H), 7.22–7.14
(m, 2 H), 2.25 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 164.3, 150.7, 140.1, 131.5, 129.5,
128.9, 128.0, 126.0, 121.6.
13C NMR (75 MHz, CDCl3): d = 164.8, 149.5, 133.5, 131.1, 130.3,
Phenyl 2-Chlorobenzoate (3ha)30
130.1, 129.5, 128.6, 126.9, 126.0, 121.9, 16.2.
1H NMR (300 MHz, CDCl3): d = 8.04 (d, J = 7.8 Hz, 1 H), 7.52–
7.42 (m, 5 H), 7.29–7.24 (m, 3 H).
m-Tolyl Benzoate (3ac)23
1H NMR (300 MHz, CDCl3): d = 8.21 (d, J = 7.2 Hz, 2 H), 7.67–
7.62 (m, 1 H), 7.54–7.49 (m, 2 H), 7.34–7.29 (m, 1 H), 7.10–7.01
(m, 3 H), 2.40 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 164.1, 150.7, 134.3, 133.1, 131.8,
131.3, 129.5, 129.3, 126.7, 126.0, 121.6.
Phenyl 3-Chlorobenzoate (3ia)27
13C NMR (75 MHz, CDCl3): d = 165.3, 150.9, 139.6, 133.5, 130.1,
129.7, 129.2, 128.5, 126.6, 122.3, 118.6, 21.3.
1H NMR (300 MHz, CDCl3): d = 8.19 (s, 1 H), 8.10 (d, J = 7.8 Hz,
1 H), 7.63–7.60 (m, 1 H), 7.49–7.42 (m, 3 H), 7.32–7.20 (m, 3 H).
3,5-Dimethylphenyl Benzoate (3ad)24
13C NMR (75 MHz, CDCl3): d = 163.9, 150.7, 134.7, 133.6, 131.3,
1H NMR (300 MHz, CDCl3): d = 8.20 (d, J = 8.1 Hz, 2 H), 7.63–
7.61 (m, 1 H), 7.53–7.48 (m, 2 H), 6.91 (s, 1 H), 6.84 (s, 2 H), 2.35
(s, 6 H).
130.1, 129.9, 129.5, 128.2, 126.0, 121.5.
Phenyl 4-Bromobenzoate (3ja)31
1H NMR (300 MHz, CDCl3): d = 8.06 (d, J = 8.5 Hz, 2 H), 7.65 (d,
J = 8.5 Hz, 2 H), 7.46–7.41 (m, 2 H), 7.31–7.19 (m, 3 H).
13C NMR (75 MHz, CDCl3): d = 165.3, 150.8, 139.3, 133.4, 130.1,
129.7, 128.5, 127.6, 119.2, 21.2.
13C NMR (75 MHz, CDCl3): d = 164.5, 150.7, 131.9, 131.6, 129.5,
128.8, 128.4, 126.0, 121.6.
Naphthalen-1-yl Benzoate (3ae)25
1H NMR (300 MHz, CDCl3): d = 8.36 (d, J = 7.8 Hz, 2 H), 7.94–
7.90 (m, 2 H), 7.82–7.68 (m, 2 H), 7.61–7.50 (m, 5 H), 7.39 (d, J =
7.7 Hz, 1 H).
Phenyl 3-Nitrobenzoate (3ka)32
1H NMR (300 MHz, CDCl3): d = 9.04 (s, 1 H), 8.54–8.48 (m, 2 H),
7.74 (m, 2 H), 7.46 (m, 2 H), 7.34–7.23 (m, 2 H).
13C NMR (75 MHz, CDCl3): d = 165.2, 146.8, 134.7, 133.8, 130.3,
129.4, 128.7, 128.0, 126.9, 126.49, 126.46, 126.1, 125.5, 121.2,
118.2.
13C NMR (75 MHz, CDCl3): d = 163.0, 150.4, 135.7, 131.3, 129.8,
139.63, 129.61, 127.9, 126.3, 125.0, 121.4.
Phenyl 4-Methylbenzoate (3ba)6a
Phenyl Cinnamate (3la)27
1H NMR (300 MHz, CDCl3): d = 8.11 (d, J = 8.2 Hz, 2 H), 7.46–
7.41 (m, 2 H), 7.33–7.20 (m, 5 H), 2.46 (s, 3 H).
1H NMR (300 MHz, CDCl3): d = 7.88 (d, J = 16.0 Hz, 1 H), 7.61–
7.58 (m, 2 H), 7.44–7.39 (m, 5 H), 7.28–7.23 (m, 1 H), 7.17 (d, J =
7.9 Hz, 2 H), 6.64 (d, J = 16.0 Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 165.2, 151.0, 144.4, 130.2, 129.4,
129.3, 126.8, 125.8, 121.8, 21.7.
13C NMR (75 MHz, CDCl3): d = 165.4, 150.8, 146.5, 134.2, 130.6,
129.4, 128.9, 128.3, 125.7, 121.6, 117.3.
Synthesis 2010, No. 12, 2005–2010 © Thieme Stuttgart · New York

PAPER
Esterification of Arenecarboxylic Acids with Trimethoxysilanes
2009
Vinyl Cinnamate (3lf)33
Acknowledgment
1H NMR (300 MHz, CDCl3): d = 7.80 (d, J = 16.0 Hz, 1 H), 7.56–
7.54 (m, 2 H), 7.46–7.40 (m, 4 H), 6.46 (d, J = 16.0 Hz, 1 H), 4.98
(d, J = 13.9 Hz, 1 H), 4.64 (d, J = 6.2 Hz, 1 H).
We thank the National Natural Science Foundation of China (No.
20972115) and the Key Project of Chinese Ministry of Education
(No. 209054) for financial support.
13C NMR (125 MHz, CDCl3): d = 163.9, 146.6, 141.2, 134.0, 130.7,
128.9, 128.2, 116.6, 97.7.
References
Naphthalen-1-yl 2-Phenylacetate (3me)34
1H NMR (300 MHz, CDCl3): d = 7.85 (d, J = 8.0 Hz, 1 H), 7.73 (d,
J = 8.2 Hz, 1 H), 7.60–7.39 (m, 9 H), 7.26–7.22 (m, 1 H), 4.03 (s, 2
H).
13C NMR (125 MHz, CDCl3): d = 169.9, 146.5, 134.6, 133.5, 129.4,
128.8, 127.9, 127.5, 126.7, 126.43, 126.41, 126.0, 125.3, 121.0,
118.0, 41.6.
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Vinyl 4-Methylbenzoate (3bf)35
1H NMR (300 MHz, CDCl3): d = 8.00 (d, J = 8.2 Hz, 2 H), 7.51 (dd,
J1 = 14.0, J2 = 6.3 Hz, 1 H), 7.28–7.26 (m, 2 H), 5.06 (dd, J1 = 14.0,
J2 = 1.5 Hz, 1 H), 4.69 (dd, J1 = 6.3, J2 = 1.5 Hz, 1 H), 3.88 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 163.7, 144.4, 141.5, 130.0, 129.2,
97.9, 21.6.
Vinyl 2-Methylbenzoate (3cf)36
1H NMR (300 MHz, CDCl3): d = 8.01 (d, J = 7.6 Hz, 1 H), 7.50 (dd,
J1 = 13.9, J2 = 6.2 Hz, 1 H), 7.46–7.42 (m, 1 H), 7.30–7.26 (m, 2 H),
5.04 (dd, J1 = 13.9, J2 = 1.5 Hz, 1 H), 4.69 (dd, J1 = 6.2, J2 = 1.5 Hz,
1 H), 2.63 (s, 3 H).
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Transl.) 2008, 44, 1619. (b) Oohashi, Y.; Fukumoto, K.;
Mukaiyama, T. Bull. Chem. Soc. Jpn. 2005, 78, 1508.
(c) Degani, I.; Dughera, S.; Fochi, R.; Serra, E. Synthesis
1999, 1200.
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13C NMR (125 MHz, CDCl3): d = 164.2, 141.3, 141.1, 132.6, 131.8,
130.9, 128.1, 125.8, 97.9, 21.7.
Vinyl 4-Methoxybenzoate (3ef)37
1H NMR (300 MHz, CDCl3): d = 8.07 (d, J = 8.3 Hz, 2 H), 7.52 (dd,
J1 = 14.0, J2 = 6.3 Hz, 1 H), 6.95 (d, J = 8.3 Hz, 2 H), 5.03 (dd, J1 =
14.0, J2 = 1.6 Hz, 1 H), 4.67 (dd, J1 = 6.3, J2 = 1.6 Hz, 1 H), 3.88 (s,
3 H).
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Synthesis 1991, 739. (b) Yadav, J. S.; Reddy, B. V. S.;
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Wada, Y.; Ueno, M.; Yokoyama, T.; Yokoyama, R.
Tetrahedron 2007, 63, 12695. (c) Gopinath, R.; Patel, B. K.
Org. Lett. 2000, 2, 577. (d) Barkakaty, B.; Talukdar, B.;
Patel, B. K. J. Org. Chem. 2003, 68, 2944. (e) Travis, B. R.;
Sivakumar, M.; Hollist, G. O.; Borhan, B. Org. Lett. 2003,
5, 1031. (f) Gopinath, R.; Paital, A. R.; Patel, B. K.
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13C NMR (75 MHz, CDCl3): d = 163.9, 163.3, 141.5, 132.1, 121.1,
113.8, 97.6, 55.4.
Vinyl 2-Methoxybenzoate (3ff)36
1H NMR (300 MHz, CDCl3): d = 7.90 (d, J = 7.9 Hz, 1 H), 7.51 (dd,
J1 = 14.0, J2 = 6.3 Hz, 1 H), 7.51–7.48 (m, 1 H), 7.02–7.6.98 (m, 2
H), 5.01 (dd, J1 = 14.0, J2 = 1.5 Hz, 1 H), 4.66 (dd, J1 = 6.3, J2 = 1.5
Hz, 1 H), 3.92 (s, 3 H).
13C NMR (125 MHz, CDCl3): d = 162.7, 159.9, 141.5, 134.3, 132.0,
120.2, 118.5, 112.2, 97.8, 56.0.
Vinyl 3-Nitrobenzoate (3kf)38
1H NMR (300 MHz, CDCl3): d = 8.93–8.92 (m, 1 H), 8.48–8.42 (m,
2 H), 7.73–7.67 (m, 1 H), 7.51 (dd, J1 = 13.9, J2 = 6.2 Hz, 1 H), 5.17
(dd, J1 = 13.9, J2 = 1.9 Hz, 1 H), 4.80 (dd, J1 = 6.2, J2 = 1.9 Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 161.6, 148.4, 141.1, 135.5, 130.8,
129.8, 127.9, 124.9, 99.4.
(7) Nakatani, Y.; Koizumi, Y.; Yamasaki, R.; Saito, S. Org.
Lett. 2008, 10, 2067.
Vinyl Biphenyl-2-carboxylate (3mf)39
(8) For selected references, see: (a) Lam, P. Y. S.; Clark, C. G.;
Saubern, S.; Adams, J.; Winters, M. P.; Chan, D. M. T.;
Combs, A. Tetrahedron Lett. 1998, 39, 2941. (b) Combs,
A.; Saubern, S.; Rafalski, M.; Lam, P. Y. S. Tetrahedron
Lett. 1999, 40, 1623. (c) Lam, P. Y. S.; Clark, C. G.;
Saubern, S.; Adams, J.; Averill, K. M.; Chan, D. M. T.;
Combs, A. Synlett 2000, 674. (d) Kantam, M. L.;Venkanna,
G. T.; Sridhar, C.; Sreedhar, B.; Choudary, B. M. J. Org.
Chem. 2006, 71, 9522. (e) Quach, T. D.; Batey, R. A. Org.
Lett. 2003, 5, 4397. (f) Sreedhar, B.; Venkanna, G. T.;
Kumar, K. B. S.; Balasubrahmanyam, V. Synthesis 2008,
1H NMR (300 MHz, CDCl3): d = 7.99–7.96 (m, 1 H), 7.59–7.26 (m,
9 H), 4.59–4.49 (m, 2 H).
13C NMR (75 MHz, CDCl3): d = 165.2, 143.4, 141.3, 141.0, 131.9,
131.0, 130.4, 129.2, 128.4, 128.0, 127.2, 98.1.
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synthesis.
Synthesis 2010, No. 12, 2005–2010 © Thieme Stuttgart · New York

2010
F. Luo et al.
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Synthesis 2010, No. 12, 2005–2010 © Thieme Stuttgart · New York