Carbonylative Sonogashira Coupling of Aryl Iodides with Terminal Alkynes Catalyzed by Palladium Nanoparticles

Article abstract of DOI:10.1002/jccs.201700302

A convenient and efficient method for the synthesis of α,β-alkynyl ketones from the three-component coupling of aryl iodides, terminal alkynes, and carbon monoxide (carbonylative Sonogashira coupling reaction) is successfully developed. The carbonylative Sonogashira coupling reaction proceeded smoothly under mild conditions in the presence of palladium nanoparticles to produce the corresponding α,β-alkynyl ketones in good to excellent yields.

Full text of DOI:10.1002/jccs.201700302

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Special Issue Paper
Carbonylative Sonogashira Coupling of Aryl Iodides with Terminal Alkynes Catalyzed
by Palladium Nanoparticles
a†
a†
a,b*
Xiujuan Feng, Jiliang Song and Ming Bao
a
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116023, China
School of Petroleum and Chemical Engineering, Dalian University of Technology, Panjin 124221, China
b
(Received: August 31, 2017; Accepted: October 30, 2017; DOI: 10.1002/jccs.201700302)
A convenient and efficient method for the synthesis of α,β-alkynyl ketones from the three-
component coupling of aryl iodides, terminal alkynes, and carbon monoxide (carbonylative Sono-
gashira coupling reaction) is successfully developed. The carbonylative Sonogashira coupling
reaction proceeded smoothly under mild conditions in the presence of palladium nanoparticles to
produce the corresponding α,β-alkynyl ketones in good to excellent yields.
Keywords: Palladium nanoparticles; α,β-Alkynyl ketones; Carbonylative Sonogashira coupling.
Xiujuan Feng received the B.Sc. degree from China University of Petroleum in 1997, and the Ph.D. degree
from Dalian University of Technology (DUT) in 2004. She then joined DUT as a staff member. She was a Vis-
iting Scholar at the University of Minnesota, USA, from 2014 to 2015. Her research interests include the trans-
2 2
formation and activation of CO , especially the reaction between epoxides, dienes, and CO .
Jiliang Song was born in Qingdao in 1988. He obtained the B.Sc. degree in chemistry from Dezhou University
in 2011, and the Ph.D. degree from Dalian University of Technology in 2017 under the guidance of Prof. Ming
Bao, working on the resource utilization of CO and CO in organic synthesis.
2
Ming Bao obtained the B.Sc. and M.Sc. degrees in chemistry from Northeast Normal University (NNU), in
986 and 1989, respectively. After carrying out research at NNU for 8 years, he joined the group of Prof.
Yoshinori Yamamoto at Tohoku University, Japan, from where he received the Ph.D. degree in 2001. From
001 to 2004, he conducted postdoctoral research at the National Institute of Advanced Industrial Science and
1
2
Technology (AIST), Japan, with Dr. Shigeru Shimada and Dr. Masao Shimizu. In 2005, he began his indepen-
dent career at Dalian University of Technology. His current research interests include the development of novel
synthetic methodologies using transition-metal catalysts.
*
Corresponding author. Email: mingbao@dlut.edu.cn
†
These authors contributed equally to the work.
J. Chin. Chem. Soc. 2017
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1

Special Issue Paper
Feng et al.
INTRODUCTION
limitations, various heterogeneous catalytic systems,
17
18
19
α,β-Alkynyl ketones are important carbonyl inter-
mediates in organic chemistry. They appear in many
biologically active molecules and play crucial roles as
key intermediates in the synthesis of natural products
and drug-like molecules.
ketones are generally prepared via the direct coupling
reaction of acid chlorides with alkynyl organometallic
such as Pd/C,
Pd(II)@ZrMOF-BIPY,
Pd/Fe O ,
MCM-41-2P-Pd(0),
3
4
20
21
MWCNTs-Fe O -Pd,
and
3
4
22
Ph P(CH CH O) CH /Pd, have been employed for
2
2
2
n
3
the synthesis of α,β-alkynyl ketones by carbonylative
Sonogashira coupling of aryl iodides, terminal alkynes,
and carbon monoxide. The recycling and use of the
expensive Pd catalysts was mostly achieved. However,
these catalytic systems also have many disadvantages
such as tedious catalyst preparation, the use of air-
sensitive ligands, and harsh reaction conditions. There-
fore, the development of a recyclable and reusable
catalyst system that allows efficient carbonylative Sono-
gashira coupling of aryl iodides with terminal alkynes
without any additional ligands is an important
requirement.
1–3
Traditionally, α,β-alkynyl
4
5
6
reagents such as those of silver, copper, sodium,
7
8
9
10
11
lithium, calcium, zinc, silicon, and tin. However,
these alkynyl organometallic reagents have low stability
and limited commercial availability.
Pd-catalyzed carbonylative coupling reaction of
aryl iodides, terminal alkynes, and carbon monoxide as
an alternative route for the synthesis of α,β-alkynyl
ketones has attracted considerable attention. The first
successful example of the synthesis of α,β-alkynyl
ketones via Pd-catalyzed carbonylative coupling reac-
tion of organic halides, terminal alkynes, and carbon
1
2
Recently, we have developed a convenient and
efficient method for CO /CO transformation by utiliz-
2
ing palladium nanoparticles (PdNPs) as catalyst in the
13
23–28
monoxide was reported by Tanaka et al. in 1981.
absence of a phosphine ligand.
In the course of our
However, this transformation process requires harsh
reaction conditions, such as high temperature and high
CO pressure (120 C, 80 atm). Mori et al. successfully
research on PdNP-catalyzed three-component reactions,
we have found that the carbonylative Sonogashira cou-
pling reaction of aryl iodides with terminal alkynes can
also be performed using PdNPs as the catalyst under
phosphine-ligand-free conditions to produce α,β-alkynyl
ketones (Scheme 1). To the best of our knowledge, no
systematic study has been conducted so far on the car-
bonylative Sonogashira coupling of aryl iodides with
terminal alkynes catalyzed by PdNPs. The results are
reported in this paper.
ꢀ
performed the Pd-catalyzed carbonylative Sonogashira
coupling reaction of terminal alkynes with aryl iodides
under atmospheric pressure of carbon monoxide at
room temperature with or without CuI by using aque-
14
ous ammonia as the base in tetrahydrofuran (THF).
Then, Yang et al. reported Pd-catalyzed copper-free
carbonylative Sonogashira coupling reaction under
atmospheric pressure of carbon monoxide at room tem-
1
5
perature by using water as the solvent. Recently, Cai
RESULTS AND DISCUSSION
et al. developed a recyclable and reusable PdCl (PPh ) /
In the initial study, the reaction of p-iodoanisole
(1a) with phenylacetylene (2a) in the presence of carbon
monoxide (CO) was selected as a model to optimize the
reaction conditions. The results are summarized in
Table 1. A series of palladium precatalysts, which
include PdCl , Pd(OAc) , Pd (dba) , and Pd(acac) ,
2
3 2
PEG-2000/H O system for the carbonylative Sonoga-
2
16
shira coupling reaction of aryl iodides with alkynes.
Although these homogeneous Pd-catalyzed carbonyla-
tive Sonogashira coupling reactions can be easily con-
ducted at room temperature under atmospheric
pressure of CO, the phosphine ligands in the reaction is
essential and the expensive palladium catalysts are usu-
ally not easy to separate and reuse. To overcome these
2
2
2
3
ꢀ
2
were initially tested in dioxane at 90 C using tetrabuty-
lammonium acetate (TBAAc) and triethyl amine
(NEt ) as the additive and base (entries 1–4). Among
3
the palladium precatalysts tested, Pd(acac) exhibited
2
the highest catalytic activity, affording 1-(4-methoxy-
phenyl)-3-phenylprop-2-yn-1-one (3a) in 78% yield
(entry 4). These results indicated that PdNPs generated
in situ from the newly formed Pd(0) species possessed
higher catalytic activity than those generated from
Scheme 1. PdNP-catalyzed carbonylative Sonoga-
shira coupling reaction.
2
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Coupling Catalyzed by Palladium Nanoparticles
a
Table 1. Screening of the reaction conditions for carbonylative Sonagashira coupling
b
Entry
Catalyst
PdCl2
Additive
Base
Solvent
Yield (%)
1
2
3
4
5
6
7
8
TBAAc
TBAAc
TBAAc
TBAAc
None
TBAF
TBAC
TBAB
TBAI
TBAAc
TBAAc
TBAAc
TBAAc
TBAAc
TBAAc
TBAAc
TBAAc
TBAAc
TBAAc
TBAAc
TBAAc
TBAAc
TBAAc
TBAAc
Et N
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Toluene
Hexane
THF
71
75
68
78
3
Pd(OAc)
Pd (dba)
2
Et
Et
3
3
N
N
2
3
Pd(acac)2
Pd(acac)2
Et N
3
c
Et N
NR
3
Pd(acac)
2
Et
3
N
65
37
49
29
74
71
76
61
58
69
61
71
75
71
76
59
78
61
77
Pd(acac)2
Pd(acac)2
Et N
3
Et N
3
9
Pd(acac)
2
3
Et N
d
1
1
1
1
1
1
1
1
1
1
2
2
2
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
Pd(acac)2
Pd(acac)2
Et N
3
e
Et N
3
Pd(acac)
2
3
n-Pr N
t
Pd(acac)2
Pd(acac)2
KO Bu
Na CO3
2
Pd(acac)
2
3
Et N
Pd(acac)2
Pd(acac)2
Et N
3
Et N
3
Pd(acac)
2
Et
3
N
MeCN
f
Pd(acac)2
Pd(acac)2
Et N
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
3
g
h
i
Et N
3
Pd(acac)
2
3
Et N
Pd(acac)2
Pd(acac)2
Et N
3
j
Et N
3
k
2
a
Pd(acac)
2
3
Et N
Reaction conditions: p-iodoanisole (1a, 117.1 mg, 0.5 mmol), phenylacetylene (2a, 61.3 mg, 0.6 mmol), CO (1.0 MPa), Pd
ꢀ
catalyst (5 mol%), additive (1.5 equiv), base (2.0 equiv), and solvent (2 mL) at 90 C for 12 h.
b
Isolated yield.
c
No reaction was observed; the starting materials were recovered.
d
1
.0 equiv of TBAAc was used.
e
f
2
.0 equiv of TBAAc was used.
ꢀ
Reaction was conducted at 50 C.
Reaction was conducted at 110 C.
Reaction was conducted at 90 C for 6 h.
g
h
i
ꢀ
ꢀ
ꢀ
Reaction was conducted at 90 C for 24 h.
j
ꢀ
ꢀ
Reaction was conducted under 0.5 MPa CO pressure at 90 C for 12 h.
k
Reaction was conducted under 2.0 MPa CO pressure at 90 C for 12 h.
Pd (dba) . The use of a quaternary ammonium salt as
additive was necessary to generate PdNPs (entry 5).
Thus, several quaternary ammonium salts (TBAAc, tet-
rabutylammonium fluoride (TBAF), tetrabutylammo-
nium chloride (TBAC), tetrabutylammonium bromide
4 and 6–9). The highest yield of the desired product 3a
was observed when TBAAc was used as the stabilizer
(entry 4, 78% yield). The amount of TBAAc required
was also investigated (entries 4, 10, and 11), and 1.5
equiv of TBAAc proved to be the most suitable
by comparing the yields with different amounts of
TBAAc.
2
3
29
(TBAB), and tetrabutylammonium iodide (TBAI)) were
then screened to determine a suitable stabilizer (entries
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Special Issue Paper
Feng et al.
Table 2. PdNP-catalyzed carbonylative Sonogashira coupling
dioxane) solvents were examined (entries 4 and 15–18),
and dioxane was found to be the optimal solvent. The reac-
tion temperature and time, as well as the CO pressure, were
finally screened using Pd(acac) , TBAAc, and NEt as the
a,b
of aryl iodides with phenylacetylene
2
3
precatalyst, additive, and base, respectively, in dioxane
entries 19–24). The results showed that the optimal reac-
(
tion temperature, reaction time, and CO pressure were
ꢀ
9
0 C, 12 h, and 1.0 MPa, respectively. Accordingly, the
subsequent Pd-catalyzed carbonylative Sonogashira cou-
plings of aryl iodides with terminal alkynes were performed
in the presence of Pd(acac) , TBAAc, and NEt as the pre-
2
3
catalyst, additive, and base in dioxane under 1.0 MPa of
ꢀ
CO pressure at 90 C for 12 h.
The carbonylative Sonogashira coupling reactions
of aryl iodides 1a–1n with phenylacetylene were per-
formed under optimum conditions, and the results are
summarized in Table 2. Good yields similar to that of
3
a were observed when 1-iodo-4-methylbenzene (1b)
and 1-iodo-2-methylbenzene (1c), which bear a methyl
group on the para or ortho positions of the benzene
ring, were employed under optimized reaction condi-
tions. The desired products, alkynyl ketones 3b and 3c,
were obtained in 82 and 79% yields, respectively. The
alkaline substrate p-iodoaniline (1d) also underwent the
target carbonylative coupling to provide the desired
product
1-(4-aminophenyl)-3-phenylprop-2-yn-1-one
a
Reaction conditions: aryl iodides (0.5 mmol),
(
3d) in 45% yield. The reason for the low yield of 3d
phenylacetylene (2a, 61.3 mg, 0.6 mmol), Pd(acac)
2
(5 mol%),
may be due to the coordination ability of amino group
to PdNP catalyst. The reactions of aryl iodides 1e–1i
with phenylacetylene also proceeded smoothly to fur-
nish the desired products 3e–3i in 71–79% yields. Nota-
bly, the halogen atoms (Cl, Br, and I) linked to the
benzene rings of the substrates were maintained in the
structures of the products (3e−3i), which suggests that
further manipulation may produce useful compounds.
Reactions of aryl iodides 1j−1l, which bear strong
electron-withdrawing groups such as trifluoromethyl
TBAAc (1.5 equiv), Et
3
N (2.0 equiv), CO (1.0 MPa), and
ꢀ
solvent (2 mL) at 90 C for 12 h.
b
Isolated yield.
The product 3a was obtained in 71% yield by using
c
recovered PdNPs.
The bases were subsequently screened using
Pd(acac) , TBAAc, and dioxane as the catalyst, addi-
2
ꢀ
tive, and solvent, respectively, at 90 C (entries 4 and
12–14). The organic base n-Pr N provided satisfactory
3
result, but could not be easily removed from the reac-
tion mixture due to its high boiling point (entry 12).
Moderate yield of the desired product 3a was obtained
(CF ), cyano (NC), and acetyl (MeCO) at the para
3
position, provided comparatively good yields for prod-
ucts 3j–3l (63, 64, and 66%, respectively). Finally, 1-
iodonaphthalene (1m) and 2-iodothiophene (1n) were
utilized in this carbonylative Sonagashira coupling reac-
tion. The desired products 3m and 3n were obtained in
71 and 75% yields.
Then, 1a was used as the iodide substrate for
determining the scope of terminal arylalkyne substrates
under the optimized reaction conditions. The results are
t
when the base KO Bu and Na CO were used (entries
2
3
13 and 14). The results described above indicate that
NEt is the best base in the carbonylative Sonogashira
3
coupling reaction. The solvents were then screened
using Pd(acac) , TBAAc, and NEt as catalyst, addi-
2
3
ꢀ
tive, and base, respectively, at 90 C. Nonpolar (toluene
and hexane) and polar (THF, acetonitrile (MeCN),
4
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Coupling Catalyzed by Palladium Nanoparticles
shown in Table 3. The reactions of 4-methylphenyl
acetylene (2b) and 3-methylphenyl acetylene (2c) pro-
ceeded smoothly to produce 4b and 4c in good yields
(84 and 83%, respectively). A good yield of the product
4d was also observed when the fluorine-substituted phe-
nylacetylene 2d was used in the carbonylative coupling
reaction (78%). The F atom linked to the benzene ring
of the substrate also was maintained in the structure of
the product. No reaction was observed when 4-
nitroethynylbenzene (2e) was tested. This behavior was
attributed to the coordination between the nitro group
and the palladium catalyst. Furthermore, a variety of
aliphatic alkyne substrates cyclopropylacetylene (2f), 1-
pentyne (2g), 3,3-dimethyl-1-butyne (2h), 1-hexyne (2i),
and 1-octyne (2j) also underwent the carbonylative cou-
pling reaction with 1a to offer the corresponding prod-
ucts 4f–4j in satisfactory to good yields (71–81%).
Fig. 1. TEM image and size distribution of PdNPs.
To gain insight into the reaction mechanism, mer-
cury (Hg) poisoning experiment was performed under
optimized reaction conditions to investigate whether the
carbonylative Sonogashira coupling reaction occurred
on the surface of the PdNPs. The target carbonylative
coupling reaction was completely inhibited in the pres-
ence of mercury. This indicated that the target reaction
30–33
Transmission electron microscopy (TEM) was used
to verify the existence of the PdNPs in the reaction mixture
occurred on the surface of the PdNPs.
A plausible mechanism for the carbonylative
Sonogashira coupling of aryl iodides with terminal
alkynes catalyzed by PdNPs is shown in Scheme 2.
PdNPs would be generated from the precatalyst
(Figure 1), which confirmed the presence of nanometer-
sized (7.83 Æ 0.59 nm) PdNPs in the reaction mixture.
The PdNPs were generated in situ from the newly formed
Pd(0) species in the presence of TBAAc as stabilizer.
34–39
Pd(acac) in the presence of the TBAAc stabilizer.
2
The oxidative addition of iodobenzene to PdNPs then
resulted in the production of the phenyl palladium
iodide intermediate A, which underwent coordination
and insertion with CO to generate the intermediate B.
Subsequent ligand exchange between the intermediate
B and a terminal alkyne occurred in the presence of a
base to produce the intermediate C, which underwent
reductive elimination to produce the target product
alkynyl ketone 3a and regenerate PdNPs.
Table 3. PdNP-catalyzed carbonylative Sonogashira coupling
a,b
of p-iodoanisole with terminal alkynes
In conclusion, we have developed a PdNP-based
catalyst system for the carbonylative Sonogashira cou-
pling of aryl iodides with terminal alkynes in the absence
of a phosphine ligand. The target reaction proceeded
smoothly to produce α,β-alkynyl ketones in satisfactory
yields (45–84%). The presented methodology has the
potential for organic synthesis considering the wide
availability of the starting materials, broad substrate
scope, experimental simplicity, and mild reaction condi-
tions (low reaction temperature and low CO pressure).
a
Reaction conditions: p-iodoanisol (1a, 117.1 mg, 0.5 mmol),
EXPERIMENTAL
General information
All reactions were performed under nitrogen
atmosphere unless otherwise noted. Solvents were
terminal alkynes (0.6 mmol), Pd(acac)
2
(5 mol%), TBAAc
(
1.5 equiv), Et
2 mL) at 90 C for 12 h.
3
N (2.0 equiv), CO (1.0 MPa), and solvent
ꢀ
(
b
Isolated yield.
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5

Special Issue Paper
Feng et al.
(
0.6 mmol), Et N (2.0 equiv), and dioxane (2 mL) were
3
placed in a 25-mL autoclave with a magnetic stirrer bar
under N atmosphere. The autoclave was purged with
2
CO three times, filled with CO to 1.0 MPa pressure, and
ꢀ
treated at 90 C for 12 h, after which it was allowed to
cool to room temperature, and the remaining CO was
vented. The resultant mixture was evaporated in vacuo to
produce the crude product, which was then purified via
silica gel chromatography (eluent: ethyl acetate/petro-
leum ether = 1:10) to afford corresponding α,β-alkynyl
ketones (see the Supporting Information).
4
0
1
-(4-Methoxyphenyl)-3-phenylprop-2-yn-1-one (3a)
Pale
1
ꢀ
yellow solid (97.9 mg, 83% yield), mp 99–100 C. H
NMR (400 MHz, CDCl ): δ 8.09 (d, J = 8.8 Hz, 2H),
3
7
.56 (d, J = 7.6 Hz, 2H), 7.38–7.29 (m, 3H), 6.88 (d,
13
J = 8.8 Hz, 2H), 3.79 (s, 3H); C NMR (100 MHz,
CDCl ): δ 176.7, 164.5, 133.0, 132.0, 130.6, 130.3,
Scheme 2. Proposed reaction mechanism.
3
1
28.7, 120.4, 113.9, 92.3, 86.9, 55.6.
purified by standard techniques without special instruc-
40
3
-Phenyl-1-(p-tolyl)prop-2-yn-1-one (3b)
Pale yellow
1
13
tions. H and C NMR spectra were recorded on a
ꢀ
1
solid (90.2 mg, 82% yield), mp 69–70 C. H NMR
400 MHz, CDCl ): δ 8.10 (d, J = 8.4 Hz, 2H), 7.66 (d,
J = 7.2 Hz, 2H), 7.51–7.36 (m, 3H), 7.29 (d,
J = 8.0 Hz, 2H), 2.43 (s, 3H); C NMR (100 MHz,
CDCl ): δ 177.7, 145.3, 134.6, 133.0, 130.7, 129.7,
1
Bruker Avance II-400 spectrometer (400 MHz for H,
(
3
13
1
00 MHz for C); CDCl and TMS were used as the
3
solvent and internal standard, respectively. The chemi-
cal shifts are reported in ppm downfield (δ) from TMS,
and the coupling constant J is given in hertz (Hz). The
peak patterns are indicated as follows: s, singlet; d, dou-
blet; t, triplet; q, quartet; m, multiplet. IR spectra were
recorded on a NEXUS FT-IR spectrometer. High-
resolution mass spectra were recorded on a Q-TOF
mass spectrometer. TEM studies were carried out on a
Tecnai G2 microscope operating at 120 kV.
13
3
1
29.4, 128.7, 120.3, 92.6, 87.0, 21.9.
40
3
-Phenyl-1-(o-tolyl)prop-2-yn-1-one (3c)
Pale yellow
1
oil (86.9 mg, 79% yield). H NMR (400 MHz, CDCl ):
δ 8.29 (dd, J = 7.6, 1.2 Hz, 1H), 7.63 (dd, J = 8.4,
.2 Hz, 2H), 7.49–7.30 (m, 5H), 7.25 (d, J = 7.6,
3
1
1
13
.2 Hz, 1H), 2.67 (s, 3H);
C NMR (100 MHz,
CDCl ): δ 179.8, 140.5, 135.7, 133.2, 133.0, 132.9,
After the carbonylative Sonogashira coupling reac-
tion of aryl iodides with terminal alkynes was performed
for 12 h at optimized reaction conditions, the resultant
mixture was used for TEM determination. Thin-layer
3
1
32.2, 130.6, 128.7, 125.9, 120.4, 91.8, 88.4, 22.0.
41
1
-(4-Aminophenyl)-3-phenylprop-2-yn-1-one (3d)
Yellow
ꢀ
1
solid (49.7 mg, 45% yield), mp 97–99 C. H NMR
chromatography (TLC) was performed on SiO (silica
2
(
400 MHz, CDCl ): δ 8.04 (d, J = 8.8 Hz, 2H), 7.62 (d,
3
gel 60 F254, Merck), and the spots were located using
UV light. Flash chromatography was performed on
J = 6.8 Hz, 2H), 7.47–7.31 (m, 3H), 6.68 (d,
13
J = 8.4 Hz, 2H), 4.48 (s, 2H). C NMR (100 MHz,
SiO (silica gel 60, 200–300 mesh). Unless otherwise
2
CDCl ): δ 176.4, 152.8, 132.9, 132.4, 130.4, 128.6,
3
noted, all starting materials were obtained from Energy
Chemical (China) and used as received. Carbon monox-
ide (99.9%) was purchased from Dalian Date Gas
Co. Ltd., China, and used without further purification.
1
27.6, 120.6, 113.8, 91.7, 87.2.
1
6
1-(4-Chlorophenyl)-3-phenylprop-2-yn-1-one (3e)
White
ꢀ
1
solid (94.8 mg, 79% yield), mp 106–107 C. H NMR
(400 MHz, CDCl ): δ 8.14 (d, J = 8.4 Hz, 2H), 7.67 (d,
3
1
3
Typical procedure for the synthesis of α,β-alkynyl ketones
J = 7.2 Hz, 2H), 7.52–7.38 (m, 5H);
C NMR
Pd(acac) (7.6 mg, 0.025 mmol), TBAAc (1.5 equiv,
(100 MHz, CDCl ): δ 176.6, 140.7, 135.3, 133.1, 131.0,
2
3
0.75 mmol), aryl iodides (0.5 mmol), terminal alkynes
130.9, 129.0, 128.8, 119.9, 93.6, 86.6.
6
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Coupling Catalyzed by Palladium Nanoparticles
4
2
1
-(2-Bromophenyl)-3-phenylprop-2-yn-1-one (3f)
Yellow
(400 MHz, CDCl ): δ 8.28 (dd, J = 6.8, 1.6 Hz, 2H),
3
1
oil (100.8 mg, 71% yield).
4
H
NMR (CDCl3,
00 MHz): δ 8.07 (dd, J = 7.6, 1.6 Hz, 1H), 7.70 (d,
J = 8.0 Hz, 1H), 7.65 (d, J = 7.2 Hz, 2H), 7.53–7.34
m, 5H); C NMR (CDCl , 100 MHz): δ 177.5, 137.5,
8.07 (dd, J = 6.8, 2.0 Hz, 2H), 7.68 (d, J = 7.2 Hz,
13
2H), 7.55–7.38 (m, 3H), 2.66 (s, 3H); C NMR
(100 MHz, CDCl ): δ 197.4, 177.1, 140.8, 139.8, 133.2,
3
13
(
131.1, 129.7, 128.8, 128.5, 119.7, 94.3, 86.8, 27.0.
3
1
1
35.0, 133.4, 133.1, 132.8, 131.0, 128.7, 127.4, 121.2,
20.0, 94.2, 88.0.
46
1
-(Naphthalen-1-yl)-3-phenylprop-2-yn-1-one (3m)
Yellow
ꢀ
1
solid (95.9 mg, 75% yield), mp 54–55 C. H NMR
(400 MHz, CDCl ): δ 9.24 (d, J = 8.8, 1H), 8.61 (dd,
J = 7.2, 1.2 Hz, 1H), 8.03 (d, J = 8.4, 1H), 7.86 (d,
J = 8.0, 1H), 7.70–7.61 (m, 3H), 7.59–7.49 (m, 2H),
7.47–7.33 (m, 3H); C NMR (100 MHz, CDCl ): δ
179.8, 135.2, 134.6, 133.9, 133.0, 132.9, 130.8, 130.7,
129.0, 128.7, 128.6, 126.8, 126.0, 124.5, 120.4,
91.8, 88.6.
4
3
1-(3-Bromophenyl)-3-phenylprop-2-yn-1-one (3g)
Yellow
3
ꢀ
1
solid (102.2 mg, 72% yield), mp 91–92 C. H NMR
400 MHz, CDCl ): δ 8.30 (d, J = 1.6 Hz, 1H), 8.14 (d,
(
3
13
J = 7.6 Hz, 1H), 7.73 (d, J = 8.0 Hz, 1H), 7.67 (d,
J = 6.8 Hz, 2H), 7.53–7.35 (m, 4H);
3
1
3
C NMR
(100 MHz, CDCl ): δ 176.4, 138.6, 136.9, 133.2, 132.3,
3
1
31.1, 130.3, 128.8, 128.1, 122.9, 119.8, 94.1, 86.5.
4
4
1
6
1
-(4-Bromophenyl)-3-phenylprop-2-yn-1-one (3h)
Yellow
3
-Phenyl-1-(thiophen-2-yl)prop-2-yn-1-one (3n)
Brown
ꢀ
1
1
ꢀ
solid (105.1 mg, 74% yield), mp 109–110 C. H NMR
solid (75.2 mg, 71% yield), mp 55–56 C. H NMR
(
7
(
400 MHz, CDCl ): δ 8.07 (d, J = 8.8 Hz, 2H),
.74–7.61 (m, 2H), 7.56–7.38 (m, 2H); C NMR
3
(400 MHz, CDCl ) δ 8.00 (d, J = 3.6 Hz, 1H), 7.72 (d,
3
1
3
J = 4.4 Hz, 1H), 7.65 (d, J = 7.2 Hz, 2H), 7.52–7.35
13
100 MHz, CDCl ): δ 176.9, 135.7, 133.1, 132.0, 131.0,
3
(m, 3H), 7.18 (t, J = 4.4 Hz, 1H);
C NMR
130.9, 129.6, 128.8, 119.9, 93.7, 86.6.
(
100 MHz, CDCl ): δ 169.8, 145.0, 135.3, 135.1, 133.1,
3
4
5
130.9, 128.7, 128.4, 120.0, 91.8, 86.5.
1
-(2-Iodophenyl)-3-phenylprop-2-yn-1-one (3i)
Yellow
1
16
oil (117.8 mg, 71% yield).
H
NMR (CDCl3,
1-(4-Methoxyphenyl)-3-(p-tolyl)prop-2-yn-1-one (4b)
White
1
400 MHz): δ 8.13 (dd, J = 7.6, 1.6 Hz, 1H), 8.05 (d,
ꢀ
solid (104.9 mg, 84% yield), mp 108–109 C. H NMR
J = 8.0 Hz, 1H), 7.65 (d, J = 7.2 Hz, 2H), 7.53–7.45
(
400 MHz, CDCl ): δ 8.17 (d, J = 8.4 Hz, 2H), 7.55 (d,
3
(
m, 2H), 7.41 (t, J = 7.6 Hz, 2H), 7.20 (td, J = 7.6,
J = 8.0 Hz, 2H), 7.19 (d, J = 8.0 Hz, 2H), 6.96 (d,
13
13
1
1
1
.2 Hz, 1H); C NMR (100 MHz, CDCl ): δ 178.1,
3
J = 8.4 Hz, 2H), 3.87 (s, 3H), 2.38 (s, 3H); C NMR
100 MHz, CDCl ): δ 176.7, 164.4, 141.3, 133.0, 131.9,
42.2, 139.4, 133.5, 133.1, 133.0, 131.0, 128.7, 128.1,
19.9, 94.4, 92.9, 87.2.
(
3
1
30.4, 129.5, 117.2, 113.9, 93.0, 86.8, 55.6, 21.7.
26
3
-Phenyl-1-(4-(trifluoromethyl)phenyl)prop-2-yn-1-one
(3j)
1
1
-(4-Methoxyphenyl)-3-(m-tolyl)prop-2-yn-1-one (4c)
Yellow
oil (103.7 mg, 83% yield). H NMR (400 MHz,
CDCl3): 8.17 (d, J = 8.8 Hz, 2H), 7.45 (d,
ꢀ
Yellow solid (90.4 mg, 66% yield), mp 72–73 C; H
NMR (400 MHz, CDCl ) δ 8.31 (d, J = 8.4 Hz, 2H),
7
1
3
δ
.77 (d, J = 8.0 Hz, 2H), 7.72–7.65 (m, 2H), 7.54–7.47
J = 5.6 Hz, 2H), 7.35–7.20 (m, 2H), 6.96 (d,
1
3
(m, 1H), 7.45–7.39 (m, 2H); C NMR (100 MHz,
13
J = 8.8 Hz, 2H), 3.86 (s, 3H), 2.35 (s, 3H); C NMR
2
CDCl ) δ 176.7, 139.4, 135.1 (q, J
1
1
= 33.0 Hz),
= 3.7 Hz),
3
C-F
(
100 MHz, CDCl ): δ 176.7, 164.5, 138.5, 133.4, 131.9,
3
3
33.2, 131.2, 129.8, 128.8, 125.7 (q, J
C-F
1
2
31.6, 130.3, 130.1, 128.6, 120.1, 113.9, 92.7, 86.7, 55.6,
1.2; IR (neat, cm ): 2925, 2841, 2191, 1767, 1724,
1
23.6 (q, J
= 271.1 Hz), 119.7, 94.5, 86.6.
−1
C-F
4
0
4
-(3-Phenylpropioloyl)benzonitrile (3k)
Yellow solid
1633, 1597, 1508, 1458, 1421, 1304, 1159, 1025,
990, 902, 844, 786, 756, 687, 599, 548; HRMS (ESI)
ꢀ
1
(
(
72.7 mg, 63% yield), mp 141–142 C; H NMR
400 MHz, CDCl ): δ 8.31 (d, J = 8.4 Hz, 2H), 7.83 (d,
+
Calcd for C H O Na: 273.0891 [M + Na] ;
3
17 14
2
J = 8.4 Hz, 2H), 7.70 (d, J = 8.0 Hz, 2H), 7.58–7.39
Found:273.0883.
13
(
m, 3H); C NMR (100 MHz, CDCl ): δ 176.2, 139.6,
47
3
3
-(4-Fluorophenyl)-1-(4-methoxyphenyl)prop-2-yn-1-one (4d)
1
9
33.3, 132.5, 131.4, 129.8, 128.9, 119.4, 117.9, 117.2,
5.1, 86.4.
ꢀ
1
White solid (99.1 mg, 78% yield). mp 105–106 C. H
NMR (400 MHz, CDCl ): δ 8.16 (d, J = 8.8 Hz, 2H),
7.66 (dd, J = 8.0, 5.6 Hz, 2H), 7.10 (dd, J = 8.8,
8.4 Hz, 2H), 6.97 (d, J = 8.8 Hz,2H), 3.88 (s, 3H);
3
4
6
1
-(4-Acetylphenyl)-3-phenylprop-2-yn-1-one (3l)
White
ꢀ
1
13
solid (79.3 mg, 64% yield), mp 82–83 C. H NMR
C
J. Chin. Chem. Soc. 2017
© 2017 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.jccs.wiley-vch.de
7

Special Issue Paper
Feng et al.
1
NMR (100 MHz, CDCl ): δ 176.5, 164.5, 163.9 (d, J
SUPPORTING INFORMATION
Additional supporting information is available in
the online version of this article.
3
3
C-
=
251.9 Hz), 135.2 (d, J
= 8.8 Hz), 131.9, 130.2,
F
C-F
4
2
1
16.4 (d, J
= 3.4 Hz), 116.2 (d, J
= 22.1 Hz),
C-F
C-F
113.9, 91.2, 86.8, 55.6.
1
6
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7
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(
8
(
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1
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NMR
3
(
3
1
1
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(
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2
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6
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-(4-Methoxyphenyl)hept-2-yn-1-one (4i)
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1
1
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(
8
87.4 mg, 81% yield). H NMR (400 MHz, CDCl ): δ
.10 (d, J = 8.4 Hz, 2H), 6.94 (d, J = 8.4 Hz, 2H), 3.88
3
(
1
s, 3H), 2.49 (t, J = 7.2 Hz, 2H), 1.70–1.60 (m, 2H),
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1
3
(
9
100 MHz, CDCl ): δ 177.0, 164.3, 131.9, 130.4, 113.7,
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1
6
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(
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96.3 mg, 79% yield). H NMR (400 MHz, CDCl ): δ
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4
(s, 3H), 2.48 (t, J = 7.2 Hz, 2H), 1.71–1.60 (m, 2H),
1
3
21. S. Yang, C. Cao, F. Wei, P. Huang, Y. Sun, W. Song,
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2
2
2
2
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ACKNOWLEDGMENTS
This work was supported by the National Natural
Science Foundation of China (Nos. 21373041 and
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2
1372035) and the Fundamental Research Funds for
the Central Universities (DUT17ZD212).
8
www.jccs.wiley-vch.de
© 2017 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J. Chin. Chem. Soc. 2017

JOURNAL OF THE CHINESE
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© 2017 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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9