One-Pot Synthesis of α,β-Unsaturated Esters, Ketones, and Nitriles from Alcohols and Phosphonium Salts

Article abstract of DOI:10.1055/s-0036-1590904

A general method for the synthesis of α,β-unsaturated esters, ketones, and nitriles is successfully achieved by a one-pot copper-catalyzed oxidation with O ₂ in air as oxidant. The solvent mixture of acetonitrile and formamide (1:1) is optimized to ensure the oxidation of alcohols, deprotonation of phosphonium salt, and Wittig reaction occur efficiently in one pot. A broad range of substrates has been explored for this process, including three electron-withdrawing group (CO ₂ Et, COPh, CN) functionalized phosphonium salts. They reacted not only with benzylic and heteroaromatic alcohols, but also with aliphatic alcohols, forming the corresponding α,β-unsaturated esters, ketones, and nitriles in moderate to excellent yields.

Full text of DOI:10.1055/s-0036-1590904

SYNTHESIS
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X
© Georg Thieme Verlag Stuttgart · New York
2017, 49, A–L
paper
A
en
W. Ding et al.
Paper
Synthesis
One-Pot Synthesis of α,β-Unsaturated Esters, Ketones, and
Nitriles from Alcohols and Phosphonium Salts
Weijie Ding
Juan Hu
EWG X–
R
• excellent isolated yield
• air or O2 as oxidant
• three steps in one pot
• copper as catalyst
• scalable
CuBr2, bipy, TEMPO, NaOH
EWG
R
OH
Ph3P
HCONH2–MeCN (1:1)
Huile Jin
49 examples
up to 99% isolated yield
Xiaochun Yu*
Shun Wang*
EWG = CO2Et, COPh, CN
X– = Cl–, Br–
R = aryl, heteroaryl, alkynyl, vinyl, alkyl
College of Chemistry and Materials Engineering, Wenzhou
University, Wenzhou, Zhejiang Province 325035, P. R. of
China
xiaochunyu@wzu.edu.cn
shunwang@wzu.edu.cn
Received: 17.07.2017
Accepted after revision: 10.08.2017
Published online: 12.09.2017
only hazardous but also difficult to handle and this further
limits their large-scale applications.
Oxygen is a more desirable oxidant from the standpoint
of green chemistry, and the use of O2 in the tandem oxida-
tion–Wittig reaction has attracted increasing attention.
Several methods have been reported, but drawbacks still
remain. For example, Chang and co-workers11 and Park and
co-workers12 both reported the ruthenium-catalyzed oxi-
dation–Wittig reaction, where noble metal catalyst Ru was
used and certain target products had low to moderate
yields. Williams and co-workers reported that N,N,N′,N′-tet-
ramethylenediamine dioxide (TMEDAO2) could be used as
co-oxidant for the tandem Ley–Griffith–Wittig reaction
with stabilized ylides, where in some cases the sequential
addition protocol was needed in order to increase reaction
yields with the use of 2 equivalents of the ylide.13 Recently,
expensive metal catalyst gold/palladium bimetallic
nanoparticles were utilized to catalyze the tandem process
of aerobic oxidation and Horner–Wadsworth–Emmons ole-
fination,14 where 1.5 equivalents of triethyl phosphonoace-
tate and 3 equivalents of base were added to promote the
reaction smoothly. Bera and co-workers reported that a di-
ruthenium complex catalyzed the dehydrogenative cou-
pling reactions of alcohols with Wittig reagents,15 where
the starting material for making the catalyst was commer-
cially unavailable, and its preparation procedure was not
easy. Therefore, developing a facile, efficient, and environ-
mentally friendly synthesis of the C=C bond using the
method of oxidation–Wittig tandem reaction is still highly
desired.
DOI: 10.1055/s-0036-1590904; Art ID: ss-2017-f0451-op
Abstract A general method for the synthesis of α,β-unsaturated es-
ters, ketones, and nitriles is successfully achieved by a one-pot copper-
catalyzed oxidation with O2 in air as oxidant. The solvent mixture of ace-
tonitrile and formamide (1:1) is optimized to ensure the oxidation of al-
cohols, deprotonation of phosphonium salt, and Wittig reaction occur
efficiently in one pot. A broad range of substrates has been explored for
this process, including three electron-withdrawing group (CO2Et, COPh,
CN) functionalized phosphonium salts. They reacted not only with ben-
zylic and heteroaromatic alcohols, but also with aliphatic alcohols,
forming the corresponding α,β-unsaturated esters, ketones, and nitriles
in moderate to excellent yields.
Key words oxidation of alcohols, phosphonium salts, tandem reac-
tion, copper catalyst, Wittig reaction, carbon–carbon double bond
The Wittig olefination reaction1 is a strategic route for
the construction of C=C bonds in organic synthesis and it
has had an enormous impact on the sophistication of the
total synthesis of organic molecules.2 However, the method
has a great limitation when applied to aldehydes due to
their instability, volatility, or unavailability. To circumvent
the use of unstable or unavailable aldehydes, the direct one-
pot oxidation–Wittig reaction of alcohols with ylides is an
attractive approach for the construction of C=C bonds. Since
the one-pot Swern oxidation–Wittig reaction reported by
Ireland and Norbeck,3 several methods for the one-pot reac-
tion of alcohols with ylides have been devised. These stud-
ies involved a large amount or a full equivalent of the oxi-
dant, such as Dess–Martin, periodinane,4 BaMnO4,5 MnO2,6
PCC,7 SO3·Py,8 or PhI(OAc)2, combined with TEMPO (cat.),9
or NMO with catalytic amount of TPAP.10 Some cases may
result in many problems, such as the formation of hazard-
ous/toxic byproducts. Certain oxidants themselves are not
Copper/TEMPO catalyst was reported by Semmelhack
and co-workers in 1984 to be effective for the oxidation of
benzylic and allylic alcohols.16 Copper-based catalysts,17
particularly those employing TEMPO18 as the redox-active
co-catalysts, have emerged as one of the most effective cat-
alysts. However, an efficient and practical Cu-catalyzed oxi-
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–L

B
W. Ding et al.
Paper
Synthesis
dation–Wittig tandem method using directly alcohols and
ylide has yet to be developed. Meanwhile, the ylide, another
starting material for the Wittig reaction, is usually provided
from the deprotonation of a phosphonium salt with base.
Whether we could use the phosphonium salt instead of the
ylide as the starting material and therefore invoke three
types of reaction (deprotonation of phosphonium salt, cata-
lytic oxidation of alcohol, and Wittig reaction) in one pot
inspired us to carry out this research. Herein, we report a
facile one-pot synthesis of α,β-unsaturated esters, ketones,
and nitriles directly from alcohols and a phosphonium salt.
Initially, in the model reaction of (2-ethoxy-2-oxoeth-
yl)triphenylphosphonium chloride (A) and (4-nitrophen-
yl)methanol (1a) the catalyst was chosen as CuBr2 (5 mol%)
with bipyridine (5 mol%) and TEMPO (5 mol%) as the co-
catalyst for the one-pot catalytic oxidation of the alcohol.18
When we used t-BuOK or NaOH as a base to abstract proton
from phosphonium salt A, and MeCN/H2O (1:1) as the sol-
vent, a poor (GC) yield of α,β-unsaturated ester 3a was ob-
tained with full conversion of 1a, while 69% or 56% of 4-ni-
trobenzaldehyde (2a) remained (Table 1, entries 1 and 2),
respectively. These results indicate that under these condi-
tions the oxidation reaction occurred efficiently, but depro-
tonation or Wittig reaction was inefficient. Then we fo-
cused on the optimization of solvent based on the anticipa-
tion that the key to our idea is to find a suitable solvent
which supports all three reactions in one pot. Results of the
solvent screening are summarized in Table 1. The various
solvents tested, such as MeCN, DMF, DMSO, 1,4-dioxane,
THF, toluene, MeOH, and HCONH2 (entries 3–10), all gave
Table 1 Solvent Screening for One-Pot Reactiona
CuBr2 (5 mol%), bipy (5 mol%)
Ph3P CH2CO2Et Cl–
4-O2NC6H4CH2OH
4-O2NC6H4CHO
+
TEMPO (5 mol%), NaOH
solvent, air
1a
A
2a
+
4-O2NC6H4CH=CHCO2Et
3a
Entry
Solvent
Yield (%)
Ratio Z/E of 3ab
1a
2a
3a
1c
2
MeCN/H2O (1:1)
MeCN/H2O (1:1)
MeCN
–
69
56
–
31
44
43
43
73
–
29:71
27:73
21:79
0:100
22:78
–
–
57
3
3
4
DMF
54
13
33
77
46
93
47
3
5
DMSO
14
67
23
25
7
6
1,4-dioxane
7
THF
–
–
8
toluene
29
–
14:86
–
9
MeOH
10
11
12
13
14
15
16
17
18
19d
20e
HCONH2
–
53
65
82
31
44
40
99
60
64
42
73
30:70
12:88
11:89
13:87
14:86
13:87
21:79
32:68
30:70
31:69
38:62
DMF/MeCN (1:1)
DMSO/MeCN (1:1)
dioxane/MeCN (1:1)
THF/MeCN (1:1)
toluene/MeCN (1:1)
HCONH2/MeCN (1:1)
HCONH2/MeCN (1:2)
HCONH2/MeCN (2:1)
HCONH2/MeCN (1:1)
HCONH2/MeCN (1:1)
32
13
57
3
5
12
53
46
1
14
–
9
31
36
58
25
–
–
2
a Reaction conditions: 100 mL Schlenk tube, alcohol 1a (1.0 mmol), A (1.1 mmol), CuBr2 (5 mol%), 2,2′-bipyridine (bipy; 5 mol%), TEMPO (5 mol%), NaOH (1.1
mmol, 1.1 equiv), solvent (2 mL), 65 °C, stirring, air balloon, 24 h.
b The Z/E ratio was determined by GC-MS.
c t-BuOK was used instead of NaOH.
d At 25 °C.
e At 40 °C.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–L

C
W. Ding et al.
Paper
Synthesis
the product of 3a in an unsatisfactory yield. Then we exam-
ined the use of mixed solvents (entries 11–18). We found
that the mixed solvent of MeCN/HCONH2 (1:1) has the best
performance. Increasing or decreasing the amount of MeCN
or HCONH2 all caused the yield of the reaction to decrease.
The reaction temperature had no significant effect on the
oxidation of alcohol which was converted into aldehyde
with full conversion even at room temperature; however, it
had a great influence on the Wittig reaction. With the de-
crease of the temperature, the yield of 3a was reduced (en-
tries 19 and 20).
Then, reactions with different NaOH loading were car-
ried out; the results are shown in Table 2. It is clear that
without the addition of NaOH, only a low yield of aldehyde
was obtained, and no Wittig product was formed. Increas-
ing the amount of NaOH resulted in higher yields of the tar-
get product 3a with more conversion of alcohol. This result
reveals that NaOH is very important for the one-pot reac-
tion which abstracts a proton from the phosphonium salt
yielding the ylide, and promotes the conversion of the alco-
hol into the aldehyde; 1.1 equivalents of NaOH are required
to ensure all three reactions occur efficiently.
(entries 16–20) and the products were isolated only in
moderate yield. The only exception is pyridin-3-ylmetha-
nol, which reacted efficiently in an excellent yield (entry
17).
Table 3 Synthesis of α,β-Unsaturated Esters from A with Alcoholsa
CuBr2 (5 mol%), bipy (5 mol%)
Ph3P CH2CO2Et Cl–
TEMPO (5 mol%)
RCH2OH
+
RCH=CHCO
2Et
NaOH, 65 °C, air or O2
HCONH2–MeCN (1:1)
3
A
Entry
1
Product 3
Yield (%)
Ratio E/Zb
CO2Et
97 (3a)
79:21
O2N
CO2Et
2
3
96 (3b)
82 (3c)
86:14
64:36
OMe
CO2Et
CO2Et
4
5
6
92 (3d)
85:15
84:16
85:15
Table 2 NaOH Loading Effect on the One-Pot Reactiona
MeO
MeO
CO2Et
Entry
NaOH (equiv) Yield (%)
Ratio Z/E
of 3ab
95 (3e)
1a
2a
3a
CO2Et
1
2
3
4
5
6
–
92
72
32
20
7
8
–
9
–
98 (3f)
90 (3g)
Cl
Cl
0.1
0.5
0.8
1.0
1.1
19
28
–
22:78
35:65
25:75
26:74
21:79
40
80
93
CO2Et
7
77:23
–
–
–
100
Cl
CO2Et
8
9
85 (3h)
91 (3i)
81:19
83:17
a Reaction conditions: 100 mL Schlenk tube, alcohol 1a (1.0 mmol), A (1.1
mmol), CuBr2 (5 mol%), 2,2′-bipyridine (5 mol%), TEMPO (5 mol%), NaOH in
solvent (2 mL), 65 °C, stirring, air balloon, 24 h.
CO2Et
b The Z/E ratio was determined by GC-MS.
Br
Br
The optimized reaction conditions were then applied to
various primary alcohols; the results are shown in Table 3.
The investigation indicates that those with reactive func-
tional groups such as bromo, chloro, and fluoro were com-
patible with the optimized reaction conditions, and no de-
halogenated product was detected by GC-MS. The substitu-
ent electronic effect of benzylic alcohols was not significant
in the reactions. All the electron-rich (4-Me, and 4-MeO)
and electron-deficient (4-NO2, 4-F, 4-Cl, and 4-Br) benzylic
alcohols reacted efficiently to give α,β-unsaturated esters in
high yield. Moreover, substituent steric effect was not sig-
nificant either, as more hindered ortho-substituted benzylic
alcohols, such as 2-MeO and 2-Cl, reacted smoothly and
formed the target products in high yield. In contrast to ben-
zyl alcohols, heterobenzyl alcohols did not react efficiently
CO2Et
CO2Et
10
11
12
13
95 (3j)
99 (3k)
93 (3l)
96 (3m)
81:19
85:15
86:14
96:4
F
CO2Et
CO2Et
O
O
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–L

D
W. Ding et al.
Paper
Synthesis
Table 3 (continued)
with 10 mol% of CuBr2 formed the corresponding products
in very good yields. It is remarkable that a highly E-selective
olefination occurs with benzyl and heterobenzyl alcohols
(4a–i), 3-phenylprop-2-en-1-ol (4k), and cyclopropylmeth-
Entry
Product 3
Yield (%)
Ratio E/Zb
14
95 (3n)
93:7
CO2Et
Table 4 Synthesis of α,β-Unsaturated Ketones from B with Alcoholsa
CO2Et
15
16
92 (3o)
56 (3p)
93:7
CuBr2 (5 mol%), bipy (5 mol%)
TEMPO (5 mol%)
Ph3P CH2COPh Br–
+
RCH2OH
RCH=CHCOPh
CO2Et
NaOH, 65 °C, air or O2
HCONH2–MeCN (1:1)
4
B
100:0
N
Entry
1
Product 4
Yield (%)
Ratio E/Zb
CO2Et
17
18
99 (3q)
69 (3r)
86:14
86:14
COPh
N
95 (4a)
96:4
O2N
CO2Et
OMe
N
COPh
2
3
4
93 (4b)
95 (4c)
93 (4d)
93:7
93:7
97:3
CO2Et
CO2Et
S
19
20
61 (3s)
71 (3t)
95:5
MeO
Cl
COPh
O
77:23
CO2Et
21c
22c
23c
69 (3u)
84 (3v)
87 (3w)
83:17
75:25
86:14
COPh
CO2Et
Cl
COPh
5
6
7
8
93 (4e)
92 (4f)
96 (4g)
94 (4h)
100:0
100:0
96:4
CO2Et
COPh
24c
25c
72 (3x)
76 (3y)
73:27
68:32
Me(CH2)6CH=CHCO2Et
COPh
COPh
O
O
CO2Et
a Reaction conditions: 100 mL Schlenk tube, alcohol 1a (1.0 mmol), A (1.1
mmol), CuBr2 (5 mol%), 2,2′-bipyridine (5 mol%), TEMPO (5 mol%), NaOH
(1.1 mmol, 1.1 equiv), solvent (2 mL), 65 °C, stirring, air balloon, 24 h.
b The E/Z ratio was determined by 1H NMR [GC (3u and 3v)].
c Under O2 with 10 mol% CuBr2.
100:0
COPh
COPh
9
10
11
95 (4i)
95 (4j)
89 (4k)
98:2
100:0
100:0
N
O
It should be mentioned that aliphatic alcohols are also
suitable substrates (Table 3, entries 21–25). When the tan-
dem reactions were conducted under optimized reaction
condition, the conversion of aliphatic alcohol into aldehyde
was very low. However, the reactions with 10 mol% of CuBr2
under an O2 atmosphere were efficient and the correspond-
ing products were obtained in moderate yields.
This method was then applied to the reaction of (2-oxo-
2-phenylethyl)triphenylphosphonium bromide (B) and al-
cohols to synthesize the corresponding α,β-unsaturated ke-
tones. As shown in Table 4, under optimized conditions the
reaction took place smoothly and gave the unsaturated ke-
tones in good to excellent yields. Similarly, the reactions of
B with aliphatic alcohols conducted under O2 conditions
COPh
COPh
12c
13c
86 (4l)
95:5
COPh
82 (4m)
86:14
a Reaction conditions: 100 mL Schlenk tube, alcohol 1a (1.0 mmol), B (1.1
mmol), CuBr2 (5 mol%), 2,2′-bipyridine (5 mol%), TEMPO (5 mol%), NaOH
(1.1 mmol, 1.1 equiv), solvent (2 mL), 65 °C, stirring, air balloon, 24 h.
b The E/Z ratio was determined by 1H NMR or GC-MS.
c Under O2 with 10 mol% CuBr2.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–L

E
W. Ding et al.
Paper
Synthesis
anol (4l) producing E-vinyl ketones. Aliphatic alcohols par-
ticipated in the reaction with B to give E-vinyl ketones with
moderate selectivity (4m).
Table 5 Synthesis of α,β-Unsaturated Nitriles from C with Alcoholsa
CuBr2 (5 mol%), bipy (5 mol%)
TEMPO (5 mol%)
Ph3P CH2CN Cl–
+
RCH2OH
RCH=CHCN
We have also examined the reaction of (cyanometh-
yl)triphenylphosphonium chloride (C) and alcohols to pre-
pare the corresponding α,β-unsaturated nitriles. As shown
in Table 5, the target products were obtained in excellent
yield. Unfortunately, aliphatic alcohols were not suitable,
and they could not be oxidized into aldehydes in the pres-
ence of C even under O2 conditions and in the presence of a
large amount of CuBr2. It should be noted that the selectivi-
ty of isomers was not good. Different from the result ob-
tained with A and B in Tables 3 and 4, Z-isomers were dom-
inant in the two isomers products of α,β-unsaturated ni-
triles with moderate Z/E selectivity. 3-Methoxybenzylic
alcohol was an exception as compound 5c was formed as a
mixture of two isomers (Z/E 40:60). It remains unclear why
Z-isomer formation for the reaction of C with alcohols is the
dominant product.
Finally, gram-scale experiments for the one-pot reac-
tion for three kinds of phosphonium salts A–C were carried
out. Thus, as shown in Scheme 1, in the cases of 5-mmol
scale reactions under the standard conditions 3a, 4a, and 5a
were afforded in 94%, 90%, and 91% isolated yields, respec-
tively, after 72 hours. The result clearly revealed the gener-
ality, practicality, and synthetic potential of this method.
NaOH, 65 °C, air
HCONH2–MeCN (1:1)
5
C
Entry
1
Product 5
Yield (%)
Ratio Z/Eb
97 (5a)
60:40
CN
O2N
OMe
2
3
4
5
96 (5b)
85:15
40:60
76:24
60:40
CN
MeO
Cl
95 (5c)
CN
94 (5d)
CN
Cl
91 (5e)
CN
6
7
98 (5f)
61:39
48:52
56:44
61:39
56:44
56:44
CN
O
O
95 (5g)
95 (5h)
93 (5i)
88 (5j)
90 (5k)
4-O2NC6H4CH=CHCO2Et
94%
A
B
CN
CN
standard
conditions
4-O2NC6H4CH2OH
+
4-O2NC6H4CH=CHCOPh
90%
8
4-O2NC6H4CH=CHCN
91%
C
9
CN
CN
Scheme 1 Gram-scale for one-pot reaction for three kinds of phospho-
nium salts
N
O
10
11
A one-pot copper-catalyzed synthesis which includes
aerobic oxidation of alcohols, deprotonation of phosphoni-
um salts, and Wittig reaction was developed in this study,
leading to high-yield production of α,β-unsaturated esters,
ketones, and nitriles. Besides the mild reaction conditions
and high isolated yields, this new procedure utilizes readily
available starting materials and is valid for a broad range of
substrates, making it very practical and convenient. Further
studies of this catalytic aerobic synthesis using other phos-
phonium salts are underway.
CN
a Reaction conditions: 100 mL Schlenk tube, alcohol 1a (1.0 mmol), C (1.1
mmol), CuBr2 (5 mol%), 2,2′-bipyridine (5 mol%), TEMPO (5 mol%), NaOH
(1.1 mmol, 1.1 equiv), solvent (2 mL), 65 °C, stirring, air balloon, 24 h.
b The Z/E ratio was determined by 1H NMR or GC-MS.
referenced to TMS (δ = 0). IR spectra were recorded on Perkin Elmer
TG-IR-GC/MS.
α,β-Unsaturated Esters 3, α,β-Unsaturated Ketones 4, and α,β-Un-
saturated Nitriles 5; General Procedure
Phosphonium salts were prepared through the reaction of Ph3P with
the corresponding halides, and other reagents were purchased from
commercial suppliers and used without further purification. Column
chromatography was carried out with silica gel (300–400 mesh).
NMR spectra were collected on 500 MHz spectrometers at r.t. in CDCl3
Alcohol (1 mmol), phosphonium salt (1.1 mmol), NaOH (1.1 mmol),
CuBr2 (5 mol%), 2,2′-bipy (5 mol%), and TEMPO (5 mol%) were mixed
in MeCN and HCONH2 (1:1, 2 mL) in a 100-mL Schlenk tube with an
air balloon, and the mixture was stirred at 65 °C for 24 h ( monitoring
by TLC and/or GC-MS). After completion, product was purified by col-
umn chromatography (EtOAc and petroleum ether).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–L

F
W. Ding et al.
Paper
Synthesis
Ethyl 3-(4-Nitrophenyl)acrylate (3a)19
White solid; yield: 214 mg (97%); mp 134–136 °C (Lit.20 138 °C).
1H NMR (500 MHz, CDCl3): δ = 7.65 (d, J = 16.0 Hz, 1 H), 7.28 (t, J = 8.0
Hz, 1 H), 7.11 (d, J = 8.0 Hz, 1 H), 7.03 (s, 1 H), 6.92 (dd, J = 2.5, 8.0 Hz,
1 H), 6.42 (d, J = 16.0 Hz, 1 H), 4.26 (q, J = 7.0 Hz, 2 H), 3.81 (s, 3 H),
1.33 (t, J = 7.0 Hz, 3 H).
13C NMR (125 MHz, CDCl3): δ = 166.8, 159.8, 144.4, 135.7, 129.7,
120.6, 118.4, 116.0, 112.8, 60.4, 55.1, 14.2.
IR: 3110.2, 3077.3, 1713.1, 1642.7, 1595.3, 1517.8, 1344.6, 1187.9,
1026.8, 977.9, 843.8, 757.8, 717.1 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 8.24 (d, J = 8.5 Hz, 2 H), 7.70–7.69 (m, 3
H), 6.57 (d, J = 16.0 Hz, 1 H), 4.30 (q, J = 7.0 Hz, 2 H), 1.36 (t, J = 7.0 Hz,
3 H).
MS (EI): m/z (%) = 206 (65), 178 (13), 177 (13), 162 (17), 161 (100),
134 (20), 133 (26), 118 (21), 90 (12), 77 (10).
13C NMR (125 MHz, CDCl3): δ = 165.8, 148.3, 141.4, 140.4, 128.5,
124.0, 122.4, 60.8, 14.1.
Ethyl 3-(4-Chlorophenyl)acrylate (3f)19
MS (EI): m/z (%) = 221 (22), 204 (12), 193 (51), 192 (10), 191 (10), 177
(12), 176 (100), 146 (18), 130 (50), 118 (13), 102 (30), 91 (11), 84 (11),
82 (16), 76 (16).
Colorless liquid; yield: 206 mg (98%).
IR: 2982.5, 2952.1, 1713.3, 1639.1, 1491.7, 1310.5, 1171.4, 1090.3,
1035.2, 821.7 cm–1
.
Ethyl 3-Phenylacrylate (3b)19
1H NMR (500 MHz, CDCl3): δ = 7.60 (d, J = 16.0 Hz, 1 H), 7.41 (d, J = 8.5
Hz, 2 H), 7.32 (d, J = 8.5 Hz, 2 H), 6.38 (d, J = 16.0 Hz, 1 H), 4.25 (q, J =
7.0 Hz, 2 H), 1.33 (t, J = 7.0 Hz, 3 H).
13C NMR (125 MHz, CDCl3): δ = 166.4, 142.8, 135.8, 132.8, 129.0,
128.9, 118.7, 60.3, 14.1.
Colorless liquid; yield: 169 mg (96%).
IR: 3107.1, 3074.2, 2981.9, 1711.5, 1538.2, 1450.3, 1366.8, 1310.6,
1269.6, 1173.9, 1037.9, 980.7, 855.8, 767.9, 712.1, 685.6 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.68 (d, J = 16.0 Hz, 1 H), 7.50–7.48 (m,
2 H), 7.35–7.34 (m, 3 H), 6.43 (d, J = 16.0 Hz, 1 H), 4.25 (q, J = 7.5 Hz, 2
H), 1.31 (t, J = 7.5 Hz, 3 H).
MS (EI): m/z (%) = 210 (34), 182 (22), 167 (33), 166 (11), 165 (100),
139 (14), 138 (20), 137 (35), 131 (10), 102 (36), 101 (31), 75 (17), 51
(10).
13C NMR (125 MHz, CDCl3): δ = 166.6, 144.2, 134.3, 129.9, 128.6,
127.8, 118.0, 60.1, 14.0.
Ethyl 3-(2-Chlorophenyl)acrylate (3g)5b
MS (EI): m/z (%) = 176 (32), 148 (15), 147 (14), 132 (11), 131 (100),
104 (13), 103 (43), 102 (10), 77 (23), 51 (9).
Colorless liquid; yield: 189 mg (90%).
IR: 3057.0, 2982.7, 1714.3, 1635.2, 1471.5, 1442.9, 1355.9, 1314.6,
1258.3, 1177.6, 1035.9, 980.0, 760.3 cm–1
.
Ethyl 3-(2-Methoxyphenyl)acrylate (3c)13
1H NMR (500 MHz, CDCl3): δ = 8.08 (d, J = 7.0 Hz, 1 H), 7.59 (dd, J = 7.5,
2.0 Hz, 1 H), 7.39 (dd, J = 7.5, 2.0 Hz, 1 H), 7.30–7.21 (m, 2 H), 6.42 (d,
J = 16.0 Hz, 1 H), 4.27 (q, J = 7.0 Hz, 2 H), 1.34 (t, J = 7.0 Hz, 3 H).
13C NMR (125 MHz, CDCl3): δ = 166.2, 140.1, 134.7, 132.6, 130.8,
130.0, 127.4, 126.9, 120.8, 60.5, 14.1.
Colorless liquid; yield: 169 mg (82%).
IR: 2979.5, 2907.1, 2834.4, 1707.3, 1631.3, 1438.8, 1453.8, 1316.2,
1247.9, 1160.1, 1027.1, 999.5, 751.8 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.99 (d, J = 16.0 Hz, 1 H), 7.49 (d, J = 8.0
Hz, 1 H), 7.34–7.23 (m, 1 H), 6.95–6.84 (m, 2 H), 6.52 (d, J = 16.0 Hz, 1
H), 4.25 (q, J = 7.0 Hz, 2 H), 3.85 (s, 3 H), 1.32 (t, J = 7.0 Hz, 3 H).
MS (EI): m/z (%) = 210 (12), 175 (52), 167 (10), 165 (31), 148 (9), 147
(100), 137 (22), 103 (18), 102 (20), 101 (27), 75 (15), 51 (8).
13C NMR (125 MHz, CDCl3): δ = 166.6, 157.5, 139.1, 130.6, 128.1,
122.6, 119.9, 117.9, 110.3, 59.5, 54.6, 13.6.
Ethyl 3-(3-Chlorophenyl)acrylate (3h)5b
MS (EI): m/z (%) = 206 (55), 176 (11), 175 (100), 162 (11), 161 (97),
147 (95), 146 (19), 133 (10), 132 (16), 131 (27), 119 (22), 118 (35),
105 (38), 103 (23), 91 (24), 90 (15), 89 (18), 79 (14), 77 (29), 63 (10),
51 (10).
Colorless liquid; yield: 179 mg (85%).
IR: 3055.0, 2982.3, 1712.6, 1640.7, 1556.3, 1311.9, 1269.9, 1199.9,
1177.2, 880.8, 860.3, 786.7, 673.6 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.59 (d, J = 16.0 Hz, 1 H), 7.48 (s, 1 H),
7.43–7.27 (m, 3 H), 6.42 (d, J = 16.0 Hz, 1 H), 4.26 (q, J = 7.0 Hz, 2 H),
1.33 (t, J = 7.0 Hz, 3 H).
13C NMR (125 MHz, CDCl3): δ = 166.3, 142.7, 136.1, 134.7, 129.9,
129.8, 127.6, 126.0, 119.6, 60.5, 14.1.
Ethyl 3-(4-Methoxyphenyl)acrylate (3d)14
Colorless liquid; yield: 190 mg (92%).
IR: 2980.4, 2839.8, 1705.3, 1533.8, 1508.7, 1250.4, 1160.7, 1029.8,
983.0, 827.9 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.63 (d, J = 16.0 Hz, 1 H), 7.45 (d, J = 8.5
Hz, 2 H), 6.88 (d, J = 8.5 Hz, 2 H), 6.30 (d, J = 16.0 Hz, 1 H), 4.24 (q, J =
7.0 Hz, 2 H), 3.80 (s, 3 H), 1.32 (t, J = 7.0 Hz, 3 H).
MS (EI): m/z (%) = 212 (10), 210 (34), 182 (20), 181 (11), 167 (33), 166
(11), 165 (100), 139 (12), 138 (14), 137 (33), 131 (12), 102 (39), 101
(28), 75 (16), 51 (10).
13C NMR (125 MHz, CDCl3): δ = 167.0, 161.1, 144.0, 129.4, 126.9,
115.5, 114.1, 60.0, 55.1, 14.1.
Ethyl 3-(4-Bromophenyl)acrylate (3i)13
Colorless liquid; yield: 231 mg (91%).
MS (EI): m/z (%) = 206 (63), 178 (12), 162 (11), 161 (100), 134 (58),
IR: 2981.0, 2930.2, 1712.5, 1637.7, 1587.7, 1488.2, 1310.2, 1270.3,
133 (7), 118 (12), 90 (10), 89 (11), 77 (11).
1171.8, 1072.2, 818.3, 743.7 cm–1
.
Ethyl 3-(3-Methoxyphenyl)acrylate (3e)5b
1H NMR (500 MHz, CDCl3): δ = 7.60 (d, J = 16.0 Hz, 1 H), 7.51–7.47 (m,
2 H), 7.36 (d, J = 8.5 Hz, 2 H), 6.41 (d, J = 16.0 Hz, 1 H), 4.26 (q, J = 7.0
Hz, 2 H), 1.33 (t, J = 7.0 Hz, 3 H).
13C NMR (125 MHz, CDCl3): δ = 166.5, 143.0, 132.3, 132.0, 129.3,
124.3, 118.9, 60.5, 14.2.
Yellow liquid; yield: 196 mg (95%).
IR: 2981.2, 2837.3, 1709.3, 1638.0, 1580.9, 1255.7, 1164.1, 1087.4,
981.6, 856.8, 783.6, 679.8 cm–1
.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–L

G
W. Ding et al.
Paper
Synthesis
MS (EI): m/z (%) = 210 (8), 175 (52), 148 (10), 147 (100), 137 (23), 103
(23), 102 (25), 101 (32), 75 (22), 51 (13).
IR: 3059.9, 2980.9, 1710.2, 1633.3, 1304.9, 1262.9, 1166.8, 1040.7,
977.6, 799.5, 775.4 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 8.50 (d, J = 15.5 Hz, 1 H), 8.15 (d, J = 8.5
Hz, 1 H), 7.81 (t, J = 2.5 Hz, 2 H), 7.68 (d, J = 7.0 Hz, 1 H), 7.53–7.39 (m,
3 H), 6.49 (d, J = 16.0 Hz, 1 H), 4.29 (q, J = 7.0 Hz, 2 H), 1.35 (t, J = 7.0
Hz, 3 H).
Ethyl 3-(3-Bromophenyl)acrylate (3j)5b
Yellow liquid; yield: 241 mg (95%).
IR: 3037.2, 2981.3, 1712.0, 1539.9, 1551.0, 1311.2, 1176.8, 1085.3,
13C NMR (125 MHz, CDCl3): δ = 166.7, 141.4, 133.5, 131.6, 131.2,
980.1, 880.0, 784.7, 669.7 cm–1
.
130.3, 126.7, 126.0, 125.3, 124.8, 123.2, 120.7, 60.4, 14.2.
1H NMR (500 MHz, CDCl3): δ = 7.65 (s, 1 H), 7.59 (d, J = 16.0 Hz, 1 H),
7.49–7.41 (m, 2 H), 7.25–7.21 (m, 1 H), 6.42 (d, J = 16.0 Hz, 1 H), 4.26
(q, J = 7.0 Hz, 2 H), 1.33 (t, J = 7.0 Hz, 3 H).
MS (EI): m/z (%) = 226 (27), 181 (18), 154 (14), 153 (100), 152 (68),
151 (11), 76 (9).
13C NMR (125 MHz, CDCl3): δ = 166.3, 142.6, 136.4, 132.8, 130.5,
130.2, 126.4, 122.8, 119.6, 60.5, 14.1.
Ethyl 3-(Naphthalen-2-yl)acrylate (3o)21
White solid; yield: 208 mg (92%); mp 70–72 °C (Lit.22 70–72 °C).
IR: 3064.1, 2982.0, 1707.7, 1633.9, 1174.4, 989.9, 822.3, 752.7 cm–1
1H NMR (500 MHz, CDCl3): δ = 7.81–7.70 (m, 5 H), 7.55–7.54 (m, 1 H),
7.43–7.41 (m, 2 H), 6.49 (d, J = 16.0 Hz, 1 H), 4.26 (q, J = 7.0 Hz, 2 H),
1.32 (t, J = 7.0 Hz, 3 H).
MS (EI): m/z (%) = 255 (35), 254 (37), 227 (22), 225 (23), 210 (69), 208
(70), 182 (19), 181 (17), 147 (15), 131 (17), 130 (24), 129 (26), 103
(16), 102 (100), 101 (17), 76 (19), 75 (20), 51 (17).
.
Ethyl 3-(4-Fluorophenyl)acrylate (3k)19
13C NMR (125 MHz, CDCl3): δ = 167.0, 144.6, 134.2, 133.3, 132.0,
Colorless liquid; yield: 192 mg (99%).
129.9, 128.7, 128.6, 127.8, 127.2, 126.7, 123.5, 118.5, 60.5, 14.4.
IR: 3028.7, 2983.6, 1712.0, 1639.7, 1600.6, 1509.8, 1314.1, 1231.7,
1160.4, 1096.1, 1035.8, 982.4, 831.5 cm–1
.
MS (EI): m/z (%) = 227 (13), 226 (75), 198 (15), 197 (13), 182 (16), 181
(100), 154 (45), 153 (63), 152 (76), 151 (18), 127 (13), 126 (9), 91 (9),
77 (12), 76 (26).
1H NMR (500 MHz, CDCl3): δ = 7.64 (d, J = 16.0 Hz, 1 H), 7.51–7.48 (m,
2 H), 7.27–7.02 (m, 2 H), 6.35 (d, J = 16.0 Hz, 1 H), 4.26 (q, J = 7.0 Hz, 2
H), 1.33 (t, J = 7.0 Hz, 3 H).
13C NMR (125 MHz, CDCl3): δ = 166.6, 164.7, 162.7 (t, JC-F = 241.8 Hz),
143.0, 130.6, 130.5 (d, JC-F = 8.5 Hz), 117.9, 115.8 (d, JC-F = 21.8 Hz),
60.3, 14.1.
Ethyl (E)-3-(Pyridin-2-yl)acrylate (3p)14
Colorless liquid; yield: 99 mg (56%).
IR: 2982.3, 2908.0, 1711.6, 1545.5, 1582.1, 1317.1, 1297.6, 1260.6,
MS (EI): m/z (%) = 194 (27), 166 (20), 150 (11), 149 (100), 122 (15),
1203.6, 1161.1, 981.4, 785.3, 744.8, 599.5 cm–1
.
121 (37), 101 (34), 75 (11).
1H NMR (500 MHz, CDCl3): δ = 8.64 (d, J = 4 Hz, 1 H), 7.73–7.67 (m, 2
H), 7.43 (d, J = 7.5 Hz, 1 H), 7.28–7.25 (m, 1 H), 6.92 (d, J = 16.0 Hz, 1
H), 4.28 (q, J = 7.0 Hz, 2 H), 1.34 (t, J = 7.0 Hz, 3 H).
Ethyl 3-(4-Tolyl)acrylate (3l)14
13C NMR (125 MHz, CDCl3): δ = 166.5, 152.8, 149.9, 143.1, 136.6,
Colorless liquid; yield: 177 mg (93%).
124.0, 123.9, 122.3, 60.5, 14.1.
IR: 2981.1, 2910.4, 1711.4, 1636.1, 1310.3, 1260.4, 1154.4, 1037.7,
984.0, 813.1 cm–1
.
MS (EI): m/z (%) = 177 (21), 148 (9), 133 (36), 132 (100), 105 (45), 104
1H NMR (500 MHz, CDCl3): δ = 7.65 (d, J = 16.0 Hz, 1 H), 7.39 (d, J = 8.5
Hz, 2 H), 7.16 (d, J = 8.5 Hz, 2 H), 6.38 (d, J = 16.0 Hz, 1 H), 4.24 (q, J =
7.5 Hz, 2 H), 2.34 (s, 3 H), 1.32 (t, J = 7.5 Hz, 3 H).
(44), 79 (13), 78 (29), 51 (15).
Ethyl 3-(Pyridin-3-yl)acrylate (3q)23
13C NMR (125 MHz, CDCl3): δ = 167.0, 144.4, 140.4, 131.6, 129.4,
Yellow liquid; yield: 175 mg (99%).
127.9, 117.0, 60.2, 21.2, 14.2.
IR: 2982.5, 2905.2, 1711.7, 1541.3, 1310.9, 1254.8, 1170.7, 1025.7,
MS (EI): m/z (%) = 190 (46), 162 (15), 146 (11), 145 (100), 131 (8), 118
982.0, 805.5, 697.9, 629.9 cm–1
.
(21), 117 (32), 116 (11), 115 (34), 65 (7).
1H NMR (500 MHz, CDCl3): δ = 8.75 (d, J = 2.5 Hz, 1 H), 8.60 (dd, J = 1.5,
5.0 Hz, 1 H), 7.85 (dt, J = 1.5, 8.0 Hz, 1 H), 7.68 (d, J = 16.0 Hz, 1 H), 7.33
(dd, J = 5.0, 7.5 Hz, 1 H), 6.53 (d, J = 16.0 Hz, 1 H), 4.28 (q, J = 7.5 Hz, 2
H), 1.35 (t, J = 7.5 Hz, 3 H).
Ethyl 3-(1,3-Benzodioxol-5-yl)acrylate (3m)19
White solid; yield: 211 mg (96%); mp 57–60 °C (Lit.13 51–53 °C).
13C NMR (125 MHz, CDCl3): δ = 165.9, 150.6, 149.3, 140.5, 133.8,
129.9, 122.4, 120.1, 60.4, 13.9.
IR: 2985.9, 2908.6, 1702.4, 1631.8, 1604.0, 1492.1, 1447.1, 1236.6,
1175.3, 1032.6, 982.3, 928.2, 851.5, 806.2 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.59 (d, J = 16.0 Hz, 1 H), 7.03–6.99 (m,
2 H), 6.81 (d, J = 8.0 Hz, 1 H), 6.26 (d, J = 16.0 Hz, 1 H), 6.00 (s, 2 H),
4.25 (q, J = 7.5 Hz, 2 H), 1.33 (t, J = 7.5 Hz, 3 H).
MS (EI): m/z (%) = 177 (21), 148 (16), 133 (32), 132 (100), 131 (22),
120 (9), 105 (9), 104 (36), 78 (13), 77 (16), 51 (20).
13C NMR (125 MHz, CDCl3): δ = 167.2, 149.5, 148.3, 144.3, 128.9,
Ethyl 3-(Pyridin-4-yl)acrylate (3r)
124.3, 116.2, 108.5, 106.5, 101.5, 60.4, 14.3.
White solid; yield: 122 mg (69%); mp 64–65 °C.
IR: 3054.6, 2984.7, 2902.1, 1705.1, 1642.5, 1598.2, 1324.1, 1300.5,
MS (EI): m/z (%) = 218 (100), 174 (87), 145 (82), 147 (60), 175 (60),
148 (45), 144 (44), 146 (34), 173 (27), 220 (24).
1182.4, 1033.3, 992.9, 818.2, 558.2 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 8.65 (d, J = 6.5 Hz, 2 H), 7.60 (d, J = 16.0
Hz, 1 H), 7.37 (d, J = 6.5 Hz, 2 H), 6.61 (d, J = 16.0 Hz, 1 H), 4.29 (q, J =
7.5 Hz, 2 H), 1.35 (t, J = 7.5 Hz, 3 H).
Ethyl 3-(Naphthalen-1-yl)acrylate (3n)5b
Colorless liquid; yield: 215 mg (95%).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–L

H
W. Ding et al.
Paper
Synthesis
13C NMR (125 MHz, CDCl3): δ = 165.7, 150.3, 141.4, 122.7, 121.5, 60.7,
14.0.
IR: 2981.8, 2934.0, 1718.0, 1653.5, 1453.6, 1313.7, 1255.3, 1192.4,
1057.4, 974.8, 747.7, 698.9 cm–1
.
HRMS (ESI): m/z [M + H]+ calcd for C10H12NO2: 178.0868; found:
178.0873.
1H NMR (500 MHz, CDCl3): δ = 7.32–7.26 (m, 2 H), 7.23–7.18 (m, 3 H),
7.05–6.99 (m, 1 H), 5.86 (d, J = 16.0 Hz, 1 H), 4.19 (q, J = 7.0 Hz, 2 H),
2.78 (t, J = 7.5 Hz, 2 H), 2.55–2.51 (m, 2 H), 1.29 (t, J = 7.5 Hz, 3 H).
Ethyl 3-(Thiophen-2-yl)acrylate (3s)14
13C NMR (125 MHz, CDCl3): δ = 166.5, 148.0, 140.8, 128.4, 128.3,
126.1, 121.8, 60.1, 34.3, 33.8, 14.2.
Yellow liquid; yield: 111 mg (61%).
MS (EI): m/z (%) = 158 (7), 157 (6), 131 (7), 130 (24), 129 (5), 116 (4),
92 (8), 91 (100), 70 (5), 65 (7).
IR: 3105.5, 2981.6, 1705.7, 1525.8, 1369.5, 1305.2, 1251.5, 1160.8,
1039.7, 969.7, 855.0, 704.9 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.77 (d, J = 15.0 Hz, 1 H), 7.35 (d, J =5.0
Hz, 1 H), 7.23 (d, J = 3.5 Hz, 1 H), 7.03 (t, J = 4.5 Hz, 1 H), 6.23 (d, J =
16.0 Hz, 1 H), 4.24 (q, J = 7.5 Hz, 2 H), 1.31 (t, J = 7.5 Hz, 3 H).
Ethyl Dec-2-enoate (3x)25
Yellow liquid; yield: 142 mg (72%).
13C NMR (125 MHz, CDCl3): δ = 166.7, 139.5, 136.9, 130.7, 128.3,
IR: 2891.1, 1870.0, 1718.8, 1656.3, 1261.5, 1042.0, 858.7 cm–1
.
128.0, 126.4, 117.0, 60.4, 14.3.
1H NMR (500 MHz, CDCl3): δ = 6.99–6.93 (m, 1 H), 5.82–5.79 (m, 1 H),
4.17 (q, J = 7.5 Hz, 2 H), 2.21–2.16 (m, 2 H), 1.29–1.27 (m, 13 H), 0.87
(t, J = 7.5 Hz, 3 H).
MS (EI): m/z (%) = 182 (49), 154 (11), 138 (10), 137 (100), 110 (30),
109 (32), 65 (17).
13C NMR (125 MHz, CDCl3): δ = 166.8, 149.5, 121.2, 60.1, 32.2, 31.7,
29.1, 29.0, 28.0, 22.6, 14.3.
Ethyl 3-(Furan-2-yl)acrylate (3t)13
Yellow liquid; yield: 118 mg (71%).
MS (EI): m/z (%) = 110 (40), 101 (82), 99 (39), 96 (33), 88 (39), 84 (43),
73 (68), 69 (56), 56 (31), 55 (100).
IR: 2982.8, 2911.4, 1711.1, 1538.4, 1368.7, 1304.3, 1260.7, 1209.9,
1163.3, 1018.5, 973.3, 752.0 cm–1
.
Ethyl 5,9-Dimethyldeca-2,8-dienoate (3y)13
1H NMR (500 MHz, CDCl3): δ = 7.46 (s, 1 H), 7.42 (d, J = 15.5 Hz, 1 H),
6.59 (d, J = 3.0 Hz, 1 H), 6.46–6.45 (m, 1 H), 6.30 (d, J = 15.5 Hz, 1 H),
4.23 (q, J = 7.5 Hz, 2 H), 1.31 (t, J = 7.5 Hz, 3 H).
Colorless liquid; yield: 181 mg (76%).
IR: 2963.9, 2923.8, 1721.0, 1656.6, 1455.3, 1377.3, 1253.3, 1181.5,
13C NMR (125 MHz, CDCl3): δ = 167.0, 150.9, 144.6, 130.9, 115.9,
1043.5, 982.5, 808.3 cm–1
.
114.5, 112.2, 60.4, 14.3.
1H NMR (500 MHz, CDCl3): δ = 6.96–6.90 (m, 1 H), 5.81–5.78 (m, 1 H),
5.07–5.06 (m, 1 H), 4.19–4.13 (m, 2 H), 2.66–2.53 (m, 1 H), 2.23–2.17
(m, 1 H), 2.06–1.92 (m, 2 H), 1.67 (s, 3 H), 1.64–1.61 (m, 1 H), 1.59 (s,
3 H), 1.36–1.31 (m, 2 H), 1.29–1.26 (m, 3 H), 0.91–0.89 (m, 3 H).
MS (EI): m/z (%) = 166 (51), 138 (39), 122 (8), 121 (100), 110 (12), 94
(37), 93 (9), 92 (7), 66 (10), 65 (37), 63 (7).
Ethyl 5-Phenylpenta-2,4-dienoate (3u)19
13C NMR (125 MHz, CDCl3): δ = 166.6, 148.1, 131.4, 124.4, 122.4, 60.1,
39.6, 36.7, 32.0, 25.7, 25.5, 19.5, 17.6.
Colorless liquid; yield: 139 mg (69%).
MS (EI): m/z (%) = 136 (26), 109 (39), 95 (69), 93 (33), 86 (22), 81 (46),
74 (22), 69 (100), 67 (35), 55 (45).
IR: 2982.6, 2923.5, 1727.6, 1450.9, 1370.4, 1244.3, 1179.5, 1027.4,
859.5, 752.6, 699.1 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.47–7.43 (m, 3 H), 7.37–7.34 (m, 2 H),
7.32–7.31 (m, 1 H), 6.92–6.84 (m, 2 H), 5.99 (d, J = 15.5 Hz, 1 H), 4.23
(q, J = 7.0 Hz, 2 H), 1.32 (t, J = 7.0 Hz, 3 H).
3-(4-Nitrophenyl)-1-phenylprop-2-en-1-one (4a)26
Yellow solid; yield: 240 mg (95%); mp 163–164 °C (Lit.27 164.5 °C).
13C NMR (125 MHz, CDCl3): δ = 167.0, 144.5, 140.3, 136.0, 129.0,
128.8, 127.1, 126.2, 121.3, 60.3, 14.3.
IR: 3110.2, 2932.6, 2853.6, 1577.3, 1528.0, 1347.0, 1110.2, 856.9,
745.1, 689.1 cm–1
.
MS (EI): m/z (%) = 202 (17), 157 (18), 130 (13), 129 (100), 128 (56),
1H NMR (500 MHz, CDCl3): δ = 8.27 (d, J = 8.5 Hz, 2 H), 8.04 (d, J = 8.5
127 (16), 115 (6), 77 (7), 64 (5), 51 (6).
Hz, 2 H), 7.83–7.78 (m, 3 H), 7.66–7.61 (m, 2 H), 7.55–7.52 (m, 2 H).
13C NMR (125 MHz, CDCl3): δ = 189.6, 148.6, 141.5, 141.0, 137.5,
133.3, 128.9, 128.8, 128.6, 125.8, 124.2.
Ethyl 3-Cyclopropylacrylate (3v)24
Colorless liquid; yield: 118 mg (84%).
IR: 2830.2, 1722.0, 1672.7, 1063.4, 1041.9, 1010.4, 857.8 cm–1
MS (EI): m/z (%) = 251 (100), 250 (44), 234 (60), 204 (51), 178 (56),
177 (63), 176 (52), 175 (38), 105 (68), 77 (40).
.
1H NMR (500 MHz, CDCl3): δ = 6.41 (dd, J = 10.0, 15.5 Hz, 1 H), 5.88 (d,
J = 15.5 Hz, 1 H), 4.16 (q, J = 7.0 Hz, 2 H), 1.59–1.54 (m, 1 H), 1.27 (t, J =
7.0 Hz, 3 H), 0.95–0.91 (m, 2 H), 0.64–0.61 (m, 2 H).
3-(2-Methoxyphenyl)-1-phenylprop-2-en-1-one (4b)26
Yellow liquid; yield: 221 mg (93%).
13C NMR (125 MHz, CDCl3): δ = 165.7, 152.9, 117.2, 59.0, 13.3, 13.2,
7.6.
IR: 3052.2, 2938.8, 2838.6, 1659.1, 1596.2, 1573.5, 1488.3, 1463.4,
1315.9, 1246.9, 1212.7, 1016.5, 988.8, 816.1, 751.2, 733.1, 693.2,
586.6 cm–1
.
MS (EI): m/z (%) = 140 (21), 125 (17), 112 (100), 111 (16), 97 (74), 95
(84), 84 (40), 67 (70), 66 (14), 65 (13).
1H NMR (500 MHz, CDCl3): δ = 8.13 (d, J = 15.5 Hz, 1 H), 8.01 (d, J = 7.5
Hz, 2 H), 7.64–7.61 (m, 2 H), 7.56 (t, J = 7.0 Hz, 1 H), 7.48 (t, J = 7.5 Hz,
2 H), 7.36 (t, J = 7.5 Hz, 1 H), 6.98 (t, J = 7.5 Hz, 1 H), 6.92 (d, J = 7.5 Hz,
1 H), 3.89 (s, 3 H).
Ethyl 5-Phenylpent-2-enoate (3w)19
Colorless liquid; yield: 177 mg (87%).
13C NMR (125 MHz, CDCl3): δ = 190.2, 158.0, 139.5, 137.7, 131.7,
131.0, 128.4, 127.7, 127.6, 123.1, 122.0, 119.9, 110.5, 54.8.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–L

I
W. Ding et al.
Paper
Synthesis
MS (EI): m/z (%) = 236 (6), 207 (28), 206 (27), 205 (100), 204 (16), 177
(5), 161 (10), 160 (7), 105 (13), 77 (11).
1H NMR (500 MHz, CDCl3): δ = 8.00 (d, J = 7.0 Hz, 2 H), 7.73 (d, J = 15.5
Hz, 1 H), 7.57 (t, J = 8.0 Hz, 1 H), 7.49 (t, J = 8.0 Hz, 2 H), 7.37 (d, J =
15.5 Hz, 1 H), 7.16 (d, J = 1.5 Hz, 1 H), 7.12 (dd, J = 1.0, 8.0 Hz, 1 H),
6.84 (d, J = 8.0 Hz, 1 H), 6.02 (s, 2 H).
3-(3-Methoxyphenyl)-1-phenylprop-2-en-1-one (4c)28
13C NMR (125 MHz, CDCl3): δ = 190.3, 149.9, 148.4, 144.6, 138.4,
Yellow liquid; yield: 226 mg (95%).
132.6, 129.4, 128.5, 128.4, 125.1, 120.1, 108.6, 106.6, 101.6.
IR: 3060.4, 2937.1, 2835.9, 1662.9, 1603.0, 1578.5, 1489.4, 1450.6,
1433.7, 1254.0, 1213.8, 1158.5, 1017.0, 981.8, 850.3, 770.2, 687.4,
MS (EI): m/z (%) = 252 (22), 251 (27), 250 (61), 249 (100), 248 (47),
174 (25), 165 (40), 164 (27), 145 (41), 122 (36).
574.4 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 8.02 (d, J = 7.0 Hz, 2 H), 7.78 (d, J = 15.5
Hz, 1 H), 7.59 (t, J = 7.5 Hz, 1 H), 7.51 (t, J = 7.5 Hz, 3 H), 7.36–7.32 (m,
1 H), 7.25 (d, J = 7.5 Hz, 1 H), 7.16 (t, J = 2.0 Hz, 1 H), 6.98–6.95 (m, 1
H), 3.86 (s, 3 H).
(E)-3-(Naphthalen-2-yl)-1-phenylprop-2-en-1-one (4h)32
Yellow solid; yield: 242 mg (94%); mp 157–158 °C (Lit.33 157–158 °C).
IR: 3059.3, 2945.1, 1658.1, 1587.5, 1477.0, 1350.9, 1295.8, 1209.9,
13C NMR (125 MHz, CDCl3): δ = 190.6, 160.0, 144.8, 138.2, 136.3,
1012.7, 991.7, 823.5, 780.9, 691.1, 657.5 cm–1
.
132.8, 129.9, 128.6, 128.5, 122.5, 121.1, 116.3, 113.5, 55.4.
1H NMR (500 MHz, CDCl3): δ = 8.07 (d, J = 7.5 Hz, 2 H), 8.03 (s, 1 H),
7.99 (d, J = 15.5 Hz, 1 H), 7.89–7.84 (m, 3 H), 7.80 (d, J = 8.5 Hz, 1 H),
7.67 (s, 1 H), 7.64–7.59 (m, 1 H), 7.55–7.52 (m, 4 H).
MS (EI): m/z (%) = 237 (29), 236 (70), 235 (98), 234 (44), 207 (37), 206
(28), 205 (100), 161 (36), 105 (24), 77 (24).
13C NMR (125 MHz, CDCl3): δ = 190.5, 144.9, 138.3, 134.4, 133.3,
132.7, 132.4, 130.6, 128.7, 128.6, 128.5, 127.8, 127.3, 126.7, 123.6,
123.6, 122.2.
3-(2-Chlorophenyl)-1-phenylprop-2-en-1-one (4d)29
Yellow liquid; yield: 225 mg (93%).
MS (EI): m/z (%) = 259 (19), 258 (93), 257 (100), 229 (19), 181 (15),
153 (15), 152 (22), 128 (17), 105 (31), 77 (37).
IR: 3063.0, 2928.4, 1654.2, 1605.2, 1469.7, 1444.9, 1314.8, 1271.7,
1214.5, 1014.1, 977.8, 750.5, 691.0, 656.6, 630.3 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 8.18 (d, J = 15.5 Hz, 1 H), 8.02 (d, J = 8.0
Hz, 2 H), 7.76–7.74 (m, 1 H), 7.59 (t, J = 7.5 Hz, 1 H), 7.52–7.47 (m, 3
H), 7.44–7.42 (m, 1 H), 7.34–7.29 (m, 2 H).
1-Phenyl-3-(pyridin-3-yl)prop-2-en-1-one (4i)32
Yellow solid; yield: 198 mg (95%); mp 101–102 °C (Lit.34 101–102 °C).
13C NMR (125 MHz, CDCl3): δ = 190.3, 140.5, 137.8, 135.4, 133.2,
132.8, 131.1, 130.2, 128.6, 128.5, 127.7, 127.0, 124.7.
IR: 3062.2, 2915.6, 1650.0, 1601.4, 1309.3, 1221.5, 1014.2, 980.6,
755.8, 712.6, 680.5, 625.3, 573.4 cm–1
.
MS (EI): m/z (%) = 242 (14), 208 (17), 207 (100), 105 (15), 102 (10),
101 (13), 89 (8), 77 (24), 75 (6), 51 (10).
1H NMR (500 MHz, CDCl3): δ = 8.83 (s, 1 H), 8.60 (d, J = 3.5 Hz, 1 H),
7.80 (d, J = 7.0 Hz, 2 H), 7.93–7.91 (m, 1 H), 7.75 (d, J = 16.0 Hz, 1 H),
7.60–7.56 (m, 2 H), 7.48 (t, J = 7.5 Hz, 2 H), 7.35–7.32 (m, 1 H).
(E)-3-(3-Chlorophenyl)-1-phenylprop-2-en-1-one (4e)28
Yellow solid; yield: 225 mg (93%); mp 75–76 °C (Lit.30 75 °C).
IR: 3054.3, 2930.5, 1664.3, 1604.9, 1564.7, 1476.9, 1448.2, 1309.0,
13C NMR (125 MHz, CDCl3): δ = 189.7, 150.9, 149.8, 140.7, 137.6,
134.6, 133.0, 130.6, 128.6, 128.4, 123.8, 123.7.
MS (EI): m/z (%) = 209 (100), 208 (64), 181 (20), 180 (54), 132 (22),
105 (52), 104 (27), 78 (17), 77 (74), 51 (39).
1215.5, 1015.5, 974.8, 771.2, 685.3, 652.8, 577.8 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 8.02 (d, J = 8.5 Hz, 2 H), 7.72 (d, J = 15.5
Hz, 1 H), 7.61–7.60 (m, 2 H), 7.53–7.47 (m, 4 H), 7.37–7.32 (m, 2 H).
13C NMR (125 MHz, CDCl3): δ = 189.9, 142.9, 137.9, 136.7, 134.9,
(E)-3-(Furan-2-yl)-1-phenylprop-2-en-1-one (4j)28
Reddish liquid; yield: 188 mg (95%).
132.9, 130.2, 130.1, 128.6, 128.5, 127.8, 126.7, 123.2.
IR: 3052.7, 2933.4, 1652.5, 1600.0, 1551.1, 1283.0, 1222.8, 1012.2,
971.1, 748.6, 699.1, 638.4, 592.2 cm–1
.
MS (EI): m/z (%) = 243 (28), 242 (73), 241 (51), 207 (100), 179 (30),
105 (76), 102 (48), 101 (33), 77 (86), 51 (32).
1H NMR (500 MHz, CDCl3): δ = 8.04 (d, J = 7.5 Hz, 2 H), 7.62–7.56 (m, 2
H), 7.53–7.46 (m, 4 H), 6.72 (d, J = 3.0 Hz, 1 H), 6.52 (s, 1 H).
(E)-1-Phenyl-3-(4-tolyl)prop-2-en-1-one (4f)26
White solid; yield: 204 mg (92%); mp 95–97 °C (Lit.27 99 °C).
13C NMR (125 MHz, CDCl3): δ = 189.5, 151.4, 144.7, 137.9, 132.5,
130.4, 128.3, 128.1, 119.1, 115.9, 112.4.
MS (EI): m/z (%) = 199 (8), 198 (55), 144 (8), 141 (11), 121 (18), 115
(10), 105 (100), 77 (43), 65 (29), 51 (18).
IR: 3024.7, 2922.7, 1656.3, 1597.3, 1340.5, 1222.0, 991.7, 817.4,
774.6, 689.1 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 8.02 (d, J = 7.0 Hz, 2 H), 7.81 (d, J = 16.0
Hz, 1 H), 7.60–7.56 (m, 3 H), 7.54–7.49 (m, 3 H), 7.23 (d, J = 7.5 Hz, 2
H), 2.40 (s, 3 H).
(2E,4E)-1,5-Diphenylpenta-2,4-dien-1-one (4k)35
Yellow solid; yield: 208 mg (89%); mp 102–103 °C (Lit.35 102–103 °C).
13C NMR (125 MHz, CDCl3): δ = 190.6, 144.9, 141.0, 138.4, 132.6,
132.2, 129.7, 128.5, 128.4, 128.3, 121.1, 21.5.
IR: 3060.1, 3034.5, 1667.9, 1598.1, 1448.5, 1221.5, 971.1, 748.4, 692.0
cm–1
.
MS (EI): m/z (%) = 220 (36), 219 (45), 207 (30), 206 (27), 205 (100),
178 (27), 177 (19), 145 (33), 144 (19), 115 (22).
1H NMR (500 MHz, CDCl3): δ = 7.99 (d, J = 7.0 Hz, 2 H), 7.64–7.55 (m, 2
H), 7.51–7.48 (m, 4 H), 7.39–7.36 (m, 2 H), 7.34–7.31 (m, 1 H), 7.10 (d,
J = 14.5 Hz, 1 H), 7.06–6.99 (m, 2 H).
3-(1,3-Benzodioxol-5-yl)-1-phenylprop-2-en-1-one (4g)28
Yellow solid; yield: 242 mg (96%); mp 120–122 °C (Lit.31 122 °C).
IR: 2924.5, 2857.0, 1657.5, 1588.0, 1487.9, 1447.0, 1307.8, 1251.8,
13C NMR (125 MHz, CDCl3): δ = 190.4, 144.7, 141.8, 138.2, 136.1,
132.6, 129.1, 128.8, 128.5, 128.3, 127.2, 126.9, 125.4.
MS (EI): m/z (%) = 235 (18), 234 (100), 233 (38), 157 (22), 129 (20),
128 (34), 105 (53), 91 (32), 77 (60), 51 (24).
1215.5, 1105.5, 1018.5, 984.2, 918.4, 775.9, 698.8, 654.6, 598.6 cm–1
.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–L

J
W. Ding et al.
Paper
Synthesis
3-Cyclopropyl-1-phenylprop-2-en-1-one (4l)29
Yellow liquid; yield: 148 mg (86%).
1H NMR (500 MHz, CDCl3): δ = 7.34–7.30 (m, 2 H), 7.04 (d, J = 8.0 Hz, 1
H), 7.00–6.97 (m, 1 H), 6.94 (s, 1 H), 5.86 (d, J = 16.5 Hz, 1 H), 3.83 (s, 3
H).
13C NMR (125 MHz, CDCl3): δ = 160.0, 150.4, 134.8, 130.1, 119.9,
118.0, 116.8, 112.5, 96.6, 55.3.
IR: 3064.1, 3008.1, 1663.5, 1607.5, 1447.9, 1379.2, 1271.5, 1229.9,
1180.5, 936.3, 889.7, 771.4, 696.1, 657.5 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.93 (d, J = 8.5 Hz, 2 H), 7.54 (t , J = 7.5
Hz, 1 H), 7.46 (t, J = 7.5 Hz, 2 H), 7.02 (d, J = 15.5 Hz, 1 H), 6.55 (dd, J =
10.5, 15.5 Hz, 1 H), 1.74–1.67 (m, 1 H), 1.04–1.00 (m, 2 H), 0.75–0.72
(m, 2 H).
MS (EI): m/z (%) = 159 (42), 158 (100), 157 (53), 131 (20), 130 (33),
128 (21), 116 (15), 102 (14), 89 (17).
3-(2-Chlorophenyl)acrylonitrile (5d)37
13C NMR (125 MHz, CDCl3): δ = 189.9, 155.2, 138.2, 132.4, 128.4,
Yellow liquid; yield: 153 mg (94%).
128.3, 122.8, 15.3, 9.2.
IR: 3064.3, 2890.4, 2219.1, 1615.2, 1470.8, 1439.5, 1051.7, 1039.3,
MS (EI): m/z (%) = 157 (21), 144 (89), 129 (11), 115 (14), 105 (100), 95
(15), 77 (86), 67 (28), 65 (11), 51 (33).
965.8, 771.6, 744.1, 700.7 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 8.09–8.07 (m, 1 H), 7.56 (d, J = 12.0 Hz,
1 H), 7.46–7.44 (m, 1 H), 7.39–7.35 (m, 2 H), 5.60 (d, J = 12.0 Hz, 1 H).
13C NMR (125 MHz, CDCl3): δ = 145.2, 134.4, 131.7, 129.9, 129.0,
5,9-Dimethyl-1-phenyldeca-2,8-dien-1-one (4m)35
Yellow liquid; yield: 221 mg (82%).
127.2, 116.5, 98.1.
IR: 2965.5, 2925.5, 2873.4, 1670.7, 1620.4, 1449.0, 1378.5, 1278.8,
982.0, 758.2, 694.1 cm–1
.
MS (EI): m/z (%) = 165 (18), 163 (59), 128 (100), 101 (34), 100 (15), 77
1H NMR (500 MHz, CDCl3): δ = 7.93 (d, J = 8.0 Hz, 2 H), 7.55 (t, J = 8.0
Hz, 1 H), 7.47 (t, J = 8.0 Hz, 2 H), 7.08–7.02 (m, 1 H), 6.88 (d, J = 15.5
Hz, 1 H), 5.09 (t, J = 6.0 Hz, 1 H), 2.36–2.31 (m, 1 H), 2.19–2.13 (m, 1
H), 2.07–1.97 (m, 2 H), 1.68 (s, 3 H), 1.60 (s, 3 H), 1.43–1.37 (m, 1 H),
1.26–1.20 (m, 1 H), 1.18–1.16 (m, 1 H), 0.95 (d, J = 7.0 Hz, 3 H).
13C NMR (125 MHz, CDCl3): δ = 190.8, 148.9, 138.0, 132.5, 131.5,
128.5, 128.4, 127.1, 124.4, 40.3, 36.8, 32.2, 25.7, 25.5, 19.6, 17.6.
(14), 75 (19), 64 (13), 51 (6), 50 (19).
3-(3-Chlorophenyl)acrylonitrile (5e)38
Yellow liquid; yield: 148 mg (91%).
IR: 3055.3, 2218.1, 1619.6, 1563.5, 1476.9, 1428.2, 1079.9, 794.5,
697.4 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.74 (d, J = 7.0 Hz, 1 H), 7.70 (s, 1 H),
7.4–7.38 (m, 1 H), 7.34–7.32 (m, 1 H), 7.07 (d, J = 12.0 Hz, 1 H), 5.51
(d, J = 12.0 Hz, 1 H).
MS (EI): m/z (%) = 254 (68), 253 (30), 137 (53), 136 (100), 135 (56),
133 (74), 132 (28), 145 (19), 121 (26), 105 (96).
13C NMR (125 MHz, CDCl3): δ = 147.0, 135.2, 134.9, 130.8, 130.2,
129.0, 126.7, 116.7, 96.7.
3-(4-Nitrophenyl)acrylonitrile (5a)13
Colorless liquid; yield: 169 mg (97%).
MS (EI): m/z (%) = 165 (24), 163 (74), 128 (100), 101 (41), 100 (16), 77
IR: 3072.9, 2925.4, 2854.3, 2217.6, 1597.0, 1514.8, 1107.9, 971.9,
(17), 75 (27), 64 (19), 51 (23), 50 (29).
857.2 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 8.31 (d, J = 8.5 Hz, 2 H), 7.96 (d, J = 8.5
Hz, 2 H), 7.23 (d, J = 12.0 Hz, 1 H), 5.70 (d, J = 12.0 Hz, 1 H).
13C NMR (125 MHz, CDCl3): δ = 149.1, 147.7, 139.2, 128.1, 124.4,
3-(4-Tolyl)acrylonitrile (5f)39
Yellow liquid; yield: 140 mg (98%).
IR: 3035.7, 2924.3, 2214.9, 1608.3, 1511.7, 1181.9, 1041.4, 970.0,
825.3, 797.2, 704.1, 575.8 cm–1
.
116.9, 101.0.
1H NMR (500 MHz, CDCl3): δ = 7.71 (d, J = 8.5 Hz, 2 H), 7.24 (d, J = 8.5
Hz, 2 H), 7.08 (d, J = 12.0 Hz, 1 H), 5.37 (d, J = 12.0 Hz, 1 H), 2.39 (s, 3
MS (EI): m/z (%) = 174 (75), 173 (100), 172 (43), 144 (40), 143 (18),
128 (45), 127 (18), 116 (36), 101 (42), 77 (12).
H).
3-(2-Methoxyphenyl)acrylonitrile (5b)36
13C NMR (125 MHz, CDCl3): δ = 148.5, 141.5, 130.9, 129.5, 129.0,
117.5, 93.7, 21.5.
Yellow liquid; yield: 153 mg (96%).
IR: 3055.1, 2942.5, 2840.8, 2213.5, 1500.5, 1487.1, 1463.6, 1251.8,
MS (EI): m/z (%) = 144 (8), 143 (74), 142 (100), 141 (43), 140 (6), 139
(5), 117 (6), 116 (29), 115 (41), 114 (20).
1110.8, 1024.9, 972.3, 751.4, 582.2 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 8.09 (d, J = 7.5 Hz, 1 H), 7.58 (d, J = 12.0
Hz, 1 H), 7.41 (t, J = 7.5 Hz, 1 H), 7.03 (t, J = 7.5 Hz, 1 H), 6.92 (d, J = 8.5
Hz, 1 H), 5.42 (d, J = 12.0 Hz, 1 H), 3.85 (s, 3 H).
13C NMR (125 MHz, CDCl3): δ = 157.4, 143.6, 132.2, 128.2, 122.7,
120.6, 117.5, 110.8, 94.6, 55.5.
3-(1,3-Benzodioxol-5-yl)acrylonitrile (5g)36
White solid; yield: 164 mg (95%); mp 90–91 °C (Lit.40 94 °C).
IR: 3058.9, 2911.9, 2204.1, 1620.5, 1594.3, 1499.8, 1443.1, 1257.5,
1099.9, 1035.1, 931.7, 810.0, 626.5 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.48 (d, J = 1.5 Hz, 1 H), 7.19 (dd, J = 1.5,
8.0 Hz, 1 H), 6.91 (d, J = 12.0 Hz, 1 H), 6.84 (d, J = 8.0 Hz, 1 H), 6.02 (s, 2
H), 5.29 (d, J = 12.0 Hz, 1 H).
MS (EI): m/z (%) = 159 (100), 158 (61), 132 (34), 131 (87), 130 (61),
119 (14), 116 (21), 91 (13), 89 (20).
3-(3-Methoxyphenyl)acrylonitrile (5c)36
13C NMR (125 MHz, CDCl3): δ = 149.9, 148.2, 148.0, 128.0, 125.5,
Yellow liquid; yield: 151 mg (95%).
117.6, 108.5, 107.9, 92.4.
IR: 3063.6, 3008.2, 2838.5, 2216.7, 1619.1, 1578.2, 1480.9, 1451.1,
MS (EI): m/z (%) = 174 (8), 173 (73), 172 (100), 171 (81), 170 (13), 116
(5), 115 (4), 114 (7), 89 (4), 88 (5).
1433.2, 1260.1, 1159.6, 1040.5, 955.7, 779.9, 684.3 cm–1
.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–L

K
W. Ding et al.
Paper
Synthesis
3-(Naphthalen-2-yl)acrylonitrile (5h)36
Supporting Information
Colorless liquid; yield: 170 mg (95%).
Supporting information for this article is available online at
IR: 3050.1, 2213.9, 1615.9, 1363.2, 1159.9, 965.7, 858.0, 812.6, 750.7
https://doi.org/10.1055/s-0036-1590904.
S
u
p
p
o
nrtogI
f
rmoaitn
S
u
p
p
ortiInfogrmoaitn
cm–1
.
1H NMR (500 MHz, CDCl3): δ = 8.14 (s, 1 H), 8.03 (d, J = 8.5 Hz, 1 H),
7.90–7.79 (m, 3 H), 7.57–7.48 (m, 2 H), 7.23 (d, J = 12.0 Hz, 1 H), 5.49
(d, J = 12.0 Hz, 1 H).
13C NMR (125 MHz, CDCl3): δ = 148.5, 134.2, 132.8, 131.0, 130.3,
128.7, 128.6, 127.7, 126.7, 124.6, 117.5, 94.9.
References
(1) (a) Wittig, G.; Geissler, G. Justus Liebigs Ann. Chem. 1953, 580,
44. (b) Wittig, G.; Schollkopf, U. Chem. Ber. 1954, 87, 1318.
(2) (a) Takeda, T. Modern Carbonyl Olefination; Wiley-VCH: Wein-
heim, 2004. (b) Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89,
863. (c) Shen, Y. Acc. Chem. Res. 1998, 31, 584.
MS (EI): m/z (%) = 180 (14), 179 (100), 178 (30), 177 (8), 152 (12), 151
(15), 89 (13), 76 (22), 75 (12), 63 (14).
(3) Ireland, R. E.; Norbeck, D. W. J. Org. Chem. 1985, 50, 2198.
(4) Barrett, A. G. M.; Hamprecht, D.; Ohkubo, M. J. Org. Chem. 1997,
62, 9376.
3-(Pyridin-3-yl)acrylonitrile (5i)
Yellow liquid; yield: 121 mg (93%).
(5) (a) Shuto, S.; Niizuma, S.; Matsuda, A. J. Org. Chem. 1998, 63,
4489. (b) Gholinejad, M.; Firouzabadi, H.; Bahrami, M.; Nájera,
C. Tetrahedron Lett. 2016, 57, 3773.
(6) (a) Pillips, D. J.; Graham, A. E. Synlett 2008, 649. (b) Taylor, R. J.
K.; Reid, M.; Foot, J.; Raw, S. A. Acc. Chem. Res. 2005, 38, 851.
(c) Nakamura, M.; Mori, Y.; Okuyama, K.; Tanikawa, K.; Yasuda,
S.; Hanada, K.; Kobayashi, S. Org. Biomol. Chem. 2003, 1, 3362.
(d) Blackburn, L.; Wei, X.; Taylor, R. J. K. Chem. Commun. 1999,
1337.
(7) Bressette, A. R.; Glover, L. C. IV. Synlett 2004, 738.
(8) Crisóstomo, F. R. P.; Carrillo, R.; Martín, T.; García-Tellado, F.;
Martín, V. S. J. Org. Chem. 2005, 70, 10099.
(9) Vatèle, J. M. Tetrahedron Lett. 2006, 47, 715.
(10) MacCoss, R. N.; Blaskus, E. P.; Ley, S. V. Tetrahedron Lett. 2003,
44, 7779.
IR: 3061.5, 2219.0, 1619.8, 1587.5, 1479.9, 1418.5, 1181.2, 1119.8,
722.3, 700.3 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 8.74 (s, 1 H), 8.62 (d, J = 9.0 Hz, 1 H),
8.35 (d, J = 9.0 Hz, 1 H), 7.40–7.37 (m, 1 H), 7.14 (d, J = 12.0 Hz, 1 H),
5.59 (d, J = 12.0 Hz, 1 H).
13C NMR (125 MHz, CDCl3): δ = 151.5, 150.8, 145.0, 134.6, 129.3,
123.6, 116.6, 97.8.
HRMS (ESI): m/z [M + H]+ calcd for C8H7N: 131.0609; found:
131.0606.
3-(Furan-2-yl)acrylonitrile (5j)41
Colorless liquid; yield: 105 mg (88%).
IR: 3062.3, 2935.1, 2214.7, 1672.3, 1625.2, 1474.1, 1390.0, 1019.7,
957.0, 748.4, 592.4 cm–1
.
(11) Kim, G.; Lee, D. G.; Chang, S. Bull. Korean Chem. Soc. 2001, 22,
943.
(12) Lee, E. Y.; Kim, Y.; Lee, J. S.; Park, J. Eur. J. Org. Chem. 2009, 2943.
(13) Read, C. D. G.; Moore, P. W.; Williams, C. M. Green Chem. 2015,
17, 4537.
1H NMR (500 MHz, CDCl3): δ = 7.61 (s, 1 H), 7.07 (d, J = 3.5 Hz, 1 H),
6.98 (d, J = 12.0 Hz, 1 H), 6.57 (d, J = 3.5 Hz, 1 H), 5.26 (d, J = 12.0 Hz, 1
H).
13C NMR (125 MHz, CDCl3): δ = 149.3, 144.4, 134.2, 116.7, 114.9,
111.8, 90.6.
(14) Miyamura, H.; Suzuki, A.; Yasukawa, T.; Kobayashi, S. Adv. Synth.
Catal. 2015, 357, 3815.
(15) Dutta, I. D.; Sarbajna, A.; Pandey, P.; Rahaman, S. M. W.; Singh,
K.; Bera, J. K. Organometallics 2016, 35, 1505.
MS (EI): m/z (%) = 119 (100), 92 (26), 91 (42), 90 (60), 65 (12), 64 (60),
63 (40), 62 (10), 52 (14), 51 (9).
(16) Semmelhack, M. F.; Schmid, C. R.; Cortes, D. A.; Chou, C. S. J. Am.
Chem. Soc. 1984, 106, 3374.
5-Phenylpenta-2,4-dienenitrile (5k)41
(17) For reviews on the copper-catalyzed oxidation of alcohols, see:
(a) Ryland, B. L.; Stahl, S. S. Angew. Chem. Int. Ed. 2014, 53, 8824.
(b) Cao, Q.; Dornan, L. M.; Rogan, L.; Hughes, N. L.; Muldoon, M.
L. Chem. Commun. 2014, 50, 4524; and references therein.
(18) Cu/TEMPO catalyst systems: (a) Gamez, P.; Arends, I.; Reedijk,
J.; Sheldon, R. A. Chem. Commun. 2003, 2414. (b) Gamez, E.;
Arends, I.; Sheldon, R. A.; Reedijk, J. Adv. Synth. Catal. 2004, 346,
805. (c) Hoover, J. M.; Stahl, S. S. J. Am. Chem. Soc. 2011, 133,
16901. (d) Hoover, J. M.; Ryland, B. L.; Stahl, S. S. J. Am. Chem.
Soc. 2013, 135, 2357. (e) Ryland, B. L.; McCann, S. D.; Brunold, T.
C.; Stahl, S. S. J. Am. Chem. Soc. 2014, 136, 12166; and references
therein.
Yellow liquid; yield: 140 mg (90%).
IR: 3052.9, 3031.3, 2211.9, 1621.3, 1589.5, 1493.1, 1449.6, 988.5,
945.8, 801.7, 735.2, 689.0 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.45 (d, J = 8.5 Hz, 2 H), 7.33–7.28 (m, 3
H), 7.19–7.13 (m, 1 H), 6.93–6.85 (m, 2 H), 5.19 (d, J = 10.5 Hz, 1 H).
13C NMR (125 MHz, CDCl3): δ = 149.2, 141.6, 135.2, 129.6, 128.8,
127.5, 124.1, 116.6, 96.5.
MS (EI): m/z (%) = 155 (100), 154 (84), 140 (32), 128 (41), 127 (54),
115 (79), 102 (20), 77 (35), 63 (29), 51 (43).
(19) Leung, P. S. W.; Teng, Y.; Toy, P. H. Org. Lett. 2010, 12, 4996.
(20) Zhou, Y.; Zhou, M. X.; Chen, M.; Su, J. H.; Du, J. F.; Song, Q. L. RSC
Adv. 2015, 5, 103977.
(21) Wang, Y.; Du, G.; Gu, C.; Xing, F.; Dai, B.; He, L. Tetrahedron
2016, 72, 472.
Funding Information
Financial support from the National Natural Science Foundation of
China (No. 21302143 and 51572198) and Natural Science Foundation
of Zhejiang Province (No. LY13B020006 and LZ17E020002) is greatly
(22) Jiang, X. Y.; Hartwig, J. F. Angew. Chem. Int. Ed. 2017, 56, 8887.
(23) Xia, X.; Toy, P. H. Synlett 2015, 26, 1737.
appreciated.
N
oaitn
a
l
N
a
utra
l
Secince
F
o
u
n
d
oaitn
of
C
h
n
i
a
2(
1
3
0
2
1
4
3
N)oaitn
a
l
N
a
utra
l
Secince
F
o
u
n
d
oaitn
of
C
h
n
i
a
5(
1
5
7
2
1
9
8
N)
a
utarl
S
ecin
c
e
F
o
u
n
d
oaitn
of
Z
haei
n
j
g
Provn
i
ce
L(Y
1
3
B
0
2
0
0
0
6
N)
a
utarl
Secince
F
o
u
n
d
oaitn
of
Z
hanie
j
g
P
orvn
i
ce
L(
Z
1
7
E
0
2
0
0
0
2)
(24) Arai, S.; Koike, Y.; Hada, H.; Nishida, A. J. Org. Chem. 2010, 75,
7573.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–L

L
W. Ding et al.
Paper
Synthesis
(25) Webb, D.; Jamison, T. F. Org. Lett. 2012, 14, 2465.
(26) Yang, W.; Miao, T.; Li, P.; Wang, L. RSC Adv. 2015, 5, 95833.
(27) Kim, N.; David, W. L. Aust. J. Chem. 2017, 70, 436.
(28) Zhang, L.; Wang, A.; Wang, W.; Huang, Y.; Liu, X.; Miao, S.; Liu,
J.; Zhang, T. ACS Catal. 2015, 5, 6563.
(34) Yang, X. Y.; Jia, Y. X.; Tay, W. S.; Li, Y. X.; Pullarkata, S. A.; Leung,
P. H. Dalton Trans.. 2016, 45, 13449.
(35) Chen, S.-J.; Lu, G.-P.; Cai, C. RSC Adv. 2015, 5, 13208.
(36) Han, Y.; Song, X.; Qiu, Y.; Hao, X.; Wang, J.; Wu, X.; Liu, X.; Liang,
Y. J. Org. Chem. 2015, 80, 9200.
(29) Liang, D.; Li, X.; Lan, Q.; Huang, W.; Yuan, L.; Ma, Y. Tetrahedron
Lett. 2016, 57, 2207.
(37) Li, L.; Stimac, J. C.; Geary, L. M. Tetrahedron Lett. 2017, 58, 1379.
(38) Wang, Z.; Chang, S. Org. Lett. 2013, 15, 1990.
(39) Gu, Z.; Wang, Y.; Yao, Y.; Xia, X.; Wang, H.; Li, W. Catal. Lett.
2015, 145, 2046.
(40) Stephen, A. D.; Bruce, A. L.; Anthony, H.; Raymond, A. W.;
George, W. G. J. Org. Chem. 1979, 44, 4640.
(30) Zhu, Y. L.; Li, C.; Zhang, J. D.; She, M. Y.; Sun, W.; Wan, K.; Wang,
Y. Q.; Yin, B.; Liu, P.; Li, J. L. Org. Lett. 2015, 17, 3872.
(31) Avik, K. B.; Alakananda, H. J. RSC Adv. 2014, 4, 23287.
(32) Jiang, Q.; Jia, J.; Xu, B.; Zhao, A.; Guo, C.-C. J. Org. Chem. 2015, 80,
3586.
(41) Lanari, D.; Alonzi, M.; Ferlin, F.; Santoro, S.; Vaccaro, L. Org. Lett.
2016, 18, 2680.
(33) Xu, L. T.; Zhang, C.; He, Y. P.; Tan, L. S.; Ma, D. W. Angew. Chem.
Int. Ed.. 2016, 55, 331.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–L