A phosphine-free heterogeneous coupling of acyl chlorides with terminal alkynes catalyzed by an MCM-41-immobilized palladium complex

Article abstract of DOI:10.1039/c3nj00425b

The phosphine-free heterogeneous coupling of acyl chlorides with terminal alkynes was achieved in triethylamine at 50 °C in the presence of a 0.2 mol% 3-(2-aminoethylamino)propyl-functionalized MCM-41-immobilized palladium complex [MCM-41-2N-Pd(OAc)₂

Full text of DOI:10.1039/c3nj00425b

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A phosphine-free heterogeneous coupling of acyl
chlorides with terminal alkynes catalyzed by an
MCM-41-immobilized palladium complex
Cite this: NewJ.Chem., 2013,
37, 3137
Bin Huang, Lin Yin and Mingzhong Cai*
The phosphine-free heterogeneous coupling of acyl chlorides with terminal alkynes was achieved
in triethylamine at 50 1C in the presence of a 0.2 mol% 3-(2-aminoethylamino)propyl-functionalized
MCM-41-immobilized palladium complex [MCM-41-2N-Pd(OAc)2], yielding a variety of ynones in good
to excellent yields. This novel heterogeneous palladium catalyst can be conveniently prepared from
commercially available and cheap reagents and recycled by a simple filtration of the reaction solution,
and used for at least 10 consecutive trials without any decrease in activity. Our system not only avoids the
use of phosphine ligands, but also solves the basic problem of palladium catalyst recovery and reuse.
Received (in Porto Alegre, Brazil)
23rd April 2013,
Accepted 17th July 2013
DOI: 10.1039/c3nj00425b
www.rsc.org/njc
Hence, heterogenization of such homogeneous palladium cata-
lysts used for the synthesis of ynones is very valuable.
Introduction
The utilization of ynones is a common strategy in the synthesis
of many biologically-active compounds and heterocyclic deri-
vatives.1 Traditionally, ynones are generally prepared via the
coupling reaction of acyl chlorides with lithium acetylides;2
however, this method lacks chemical selectivity in the presence
of other electrophiles and functional groups such as hydroxyls,
acids, amines, aldehydes, ketones, etc. also have to be protected
prior to the reaction. Recently, an alternative coupling of acyl
chlorides with terminal alkynes catalyzed by palladium cata-
lysts has received much attention since this reaction can
proceed under mild conditions with a wide range of functional
groups on alkynes and enhanced chemoselectivity.3 Among
these successful examples for the construction of synthetically
useful ynones, homogeneous palladium complexes such as
PdCl2(PPh3)2 and Pd(OAc)2 are usually used as catalysts for
the coupling reactions. However, the problem with homo-
geneous catalysis is the difficulty to separate the expensive
palladium catalyst from the reaction mixture and the impossi-
bility to reuse it in consecutive reactions. From the viewpoints
of economical and environmental concern, easy separation of
catalysts and products for the recycling of the catalyst is very
important. In contrast, heterogeneous catalysts can be easily
separated from the reaction mixture by simple filtration and
reused in successive reactions provided that the active sites
have not become deactivated. Heterogeneous catalysis also
helps to minimize wastes derived from reaction workup, con-
tributing to the development of green chemical processes.4
Recently, Likhar et al. reported the coupling reaction of acyl
chlorides with terminal alkynes catalyzed by Pd/C in toluene
and found that the catalyst could be reused for five cycles
with a 15% leaching of palladium.5 Bakherad et al. described
the acylation of acyl chlorides with terminal alkynes catalyzed
by a polystyrene-supported phosphine palladium(0) complex
[PS-dpp-Pd(0)].6 This heterogeneous phosphine palladium
catalyst exhibited high catalytic activity and good reusability,
but its preparation requires use of expensive 1,2-bis(diphenyl-
phosphino)ethane (dppe). Recent developments on the meso-
porous material MCM-41 provided a new possible candidate for
a solid support for immobilization of homogeneous catalysts.7
MCM-41 has a regular pore diameter of ca. 5 nm and a specific
surface area >700 m2 gꢀ1.8 Its large pore size allows passage of
large molecules such as organic reactants and metal complexes
through the pores to reach the surface of the channel.9 To date,
some palladium complexes on the functionalized MCM-41
support have been prepared and successfully used in carbon–
carbon bond formation reactions such as Heck reaction,10
Suzuki–Miyaura reaction,11 Sonogashira reaction,12 and Stille
reaction.13 Recently, Tsai et al. reported that the nanosized
MCM-41 anchored palladium bipyridyl complex can also cata-
lyze efficiently the coupling of acyl chlorides with terminal
alkynes in the presence of a catalytic amount of PPh3.14 How-
ever, the procedure for preparing this supported palladium
catalyst is rather complicated due to the use of expensive and
not readily available 4,40-bis(bromomethyl)-2,20-bipyridine,
moreover, the catalyst exhibited very low activity without the
addition of PPh3 and only 2% GC yield was obtained. Therefore,
the development of phosphine-free, readily available heterogeneous
Department of Chemistry, Jiangxi Normal University, Nanchang 330022,
P. R. China. E-mail: mzcai@jxnu.edu.cn
c
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Table 1 XPS data for MCM-41-2N-Pd(OAc)2, MCM-41-2N, Pd(OAc)2 and metal
palladium catalysts having a high activity and good stability is a
topic of enormous importance. In continuing our efforts to
develop practical synthetic pathways for organic transforma-
tions, our new approach, described in this paper, was to design
and synthesize a 3-(2-aminoethylamino)propyl-functionalized
Pda
Sample
Pd3d5/2
337.5
N1s
Si2p
O1s
MCM-41-2N-Pd(OAc)2
MCM-41-2N
400.8
399.6
103.3
103.2
533.1
533.2
MCM-41-immobilized palladium complex, which was used as Pd(OAc)2
338.2
335.4
Metal Pd
an effective, phosphine-free palladium catalyst for the coupling
of acyl chlorides with terminal alkynes.
a
The binding energies are referenced to C1s (284.6 eV) and the energy
differences were determined with an accuracy of ꢁ0.2 eV.
Results and discussion
in metal Pd. These results show that a coordination bond
Although phosphine ligands stabilize palladium and influence between N and Pd is formed in MCM-41-2N-Pd(OAc)2.
its reactivity, the simplest and cheapest palladium catalysts are
In order to test the catalytic activity of the MCM-41-2N-
of course phosphine-free systems, specifically when used at low Pd(OAc)2, the coupling reactions of terminal alkynes with acyl
loading. It is known that the catalysts containing phosphine chlorides were investigated. The reaction of phenylacetylene
ligands are unstable at higher temperatures.15 Furthermore, with benzoyl chloride (1.1 equiv.) was chosen as a model
the procedure for preparing the polymer-immobilized phos- reaction, and the influences of various reaction parameters
phine palladium complexes is rather complicated since the such as solvent, base, and palladium catalyst quantity on the
synthesis of the supported phosphine ligands requires multi- reaction were tested. The results are summarized in Table 2.
step sequences. A novel MCM-41-immobilized bidentate nitrogen Among the temperatures evaluated [25, 50 and 80 1C], 50 1C was
palladium(II) complex [MCM-41-2N-Pd(OAc)2] was conveniently found to be the most effective. The decrease in yield upon
synthesized from commercially available and inexpensive 3-(2- enhancing the temperature may be due to the oxidative homo-
aminoethylamino)propyltrimethoxysilane via immobilization coupling of terminal alkynes in the presence of CuI. We then
on MCM-41, followed by reaction with palladium acetate in turned our attention to investigate the effect of solvents on the
acetone (Scheme 1). The X-ray powder diffraction (XRD) ana- coupling reaction. Among the solvents evaluated such as
lysis of the MCM-41-2N-Pd(OAc)2 indicated that, in addition to toluene, DME, THF, dioxane and Et3N, Et3N was the best
an intense diffraction peak (100), two higher order peaks (110) choice. The coupling reaction was completely blocked as inor-
and (200) with lower intensities were also detected, and there- ganic bases such as K2CO3 and Cs2CO3 were used, presumably
fore the chemical bonding procedure did not diminish the due to the poor solubility of these salts in organic solvents
structural ordering of the MCM-41.
(entries 8 and 9). When Et3N was used as both base and solvent,
Elemental analyses and X-ray photoelectron spectroscopy the coupling reaction proceeded very smoothly at 50 1C to afford
(XPS) were used to characterize the MCM-41-immobilized the desired coupling product in an excellent yield (entry 2). The
bidentate nitrogen palladium(II) complex. The N : Pd mole ratio amount of supported palladium catalyst was also screened, and
of the MCM-41-2N-Pd(OAc)2 was determined to be 6.22. The 0.2 mol% loading of palladium was found to be optimal; a
XPS data for MCM-41-2N-Pd(OAc)2, MCM-41-2N, Pd(OAc)2 and lower yield was observed and a longer reaction time was required
metal Pd are listed in Table 1. It can be seen that the binding when the amount of the catalyst was decreased (entry 11).
energies of Si2p and O1s of MCM-41-2N-Pd(OAc)2 are similar to Increasing the amount of palladium catalyst could shorten the
those of MCM-41-2N. However the difference of N1s binding reaction time, but did not increase the yield of 1,3-diphenyl-
energies between MCM-41-2N-Pd(OAc)2 and MCM-41-2N is propynone (entry 12). CuI as co-catalyst had to be added to
1.2 eV. The binding energy of Pd3d5/2 in MCM-41-2N-Pd(OAc)2 the reaction system to obtain a satisfactory result (entry 13), the
is 0.7 eV less than that in Pd(OAc)2, but 2.1 eV larger than that role of CuI should be the conversion of terminal alkynes to the
Scheme 1 Preparation of MCM-41-2N-Pd(OAc)2.
c
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Table 2 Reaction condition screening for the coupling reaction of phenylacetylene with benzoyl chloridea
Entry
Solvent
Base
Temp. (1C)
Time (h)
Yieldb (%)
1
2
3
4
5
6
7
8
Et3N
Et3N
Et3N
Toluene
Dioxane
DME
THF
THF
THF
THF
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
Et3N
K2CO3
Cs2CO3
DBU
Et3N
Et3N
Et3N
25
50
80
50
50
50
50
50
50
50
50
50
50
24
6
4
25
92
86
23
19
7
21
0
0
15
85
91
9
24
24
24
24
24
24
24
15
3
9
10
11c
12d
13e
24
a
Reaction conditions: phenylacetylene (1.0 mmol), benzoyl chloride (1.1 mmol), MCM-41-2N-Pd(OAc)2 (0.2 mol%), CuI (0.2 mol%), base (2.0 mmol)
b
c
d
e
in solvent (3.0 mL) under Ar. Isolated yield. 0.1 mol% of palladium catalyst was used. 0.5 mol% of palladium catalyst was used. Without CuI.
corresponding alkynyl copper(I). Thus, the optimized reaction lysts such as Pd/C (from Aldrich). The reaction of benzoyl
conditions for this coupling reaction are the MCM-41-2N- chloride (1.1 equiv.) with phenylacetylene in the presence of
Pd(OAc)2 (0.2 mol%), CuI (0.2 mol%) in Et3N with Et3N as base 0.2 mol% of Pd/C (10 wt%) and 0.2 mol% of CuI in Et3N at 50 1C
at 50 1C under Ar for 6 h (entry 2).
for 6 h gave a 75% yield of 3a.
With these promising results in hand, we started investigat-
The optimized reaction conditions were also applied to the
ing the scope of both terminal alkynes and acyl chlorides under coupling of aliphatic terminal alkynes such as 1-hexyne,
the optimized conditions, and the results are summarized 1-octyne, and 3-methoxypropyne with a variety of aromatic acyl
in Table 3. As shown in Table 3, the coupling reactions of chlorides and heteroaroyl chlorides; the results are also sum-
phenylacetylene with a variety of aromatic acyl chlorides pro- marized in Table 3. Various electron-donating and electron-
ceeded smoothly under mild conditions affording the corre- withdrawing groups such as –OCH3, –CH3, –NO2, and –Cl on
sponding ynones 3a–d in excellent yields (entries 1–4). The aromatic acyl chlorides were well tolerated to give the desired
coupling reactions of heteroaryl chlorides such as furan-2- ynones 3h–u in good to excellent yields (entries 8–21). (Tri-
carbonyl chloride and thiophene-2-carbonyl chloride with phenyl- methylsilyl)acetylene was also coupled with a variety of aromatic
acetylene gave the corresponding ynones 3e and 3f in 90% and acyl chlorides to afford the corresponding 1-aryl-3-(trimethyl-
87% yields, respectively (entries 5 and 6). The reaction of sub- silyl)propynones 3v–y in high yields (entries 22–25).
stituted phenylacetylenes such as 4-methylphenylacetylene with
The method provides a quite general route for the synthesis
benzoyl chloride also gave the desired coupled product 3g in an of ynones having various functionalities. The results above
excellent yield (entry 7). In order to compare the catalytic activity prompted us to investigate the coupling reaction of aliphatic
of this heterogeneous palladium catalyst with a homogeneous acyl chlorides with terminal alkynes, but aliphatic acyl chlorides
one, Pd(OAc)2/H2NCH2CH2NH2 (1 : 1) was used as the catalyst for were not reactive under the conditions optimized for aromatic
the reaction of phenylacetylene with benzoyl chloride. Under acyl chlorides. For example, the reaction of acetyl chloride
identical conditions, a 79% yield of 3a was isolated, indicating (2 equiv.) with phenylacetylene in Et3N in the presence of
that a higher activity was obtained after heterogenization of the 1 mol% of MCM-41-2N-Pd(OAc)2 and 1 mol% of CuI was carried
palladium catalyst as compared with its homogeneous counter- out at 50 1C for 24 h, and no desired ynone was detected. A
part. A possible explanation for the higher activity observed for the similar observation was made by Bakherad et al. in the coupling
MCM-41-2N-Pd(OAc)2 complex is that the chemical bonding reaction of acyl chlorides with terminal alkynes catalyzed by a
between metal complexes and functional groups of the MCM-41 polystyrene-supported phosphine palladium(0) complex.6
support maintains the isolated nature of metal complexes, which
In order to determine whether the catalysis was due to the
can influence the catalytic performance in a manner that the MCM-41-2N-Pd(OAc)2 complex or to a homogeneous palladium
analogous homogeneous complex does not exhibit high activity in complex that comes off the support during the reaction and
solution.16 It is generally believed that high surface area of hetero- then returns to the support at the end, we performed the hot
geneous catalyst results in high catalytic activity. In addition, the filtration test.17 We focused on the coupling reaction of phenyl-
MCM-41 support has an extremely high surface area, which also acetylene with benzoyl chloride. We filtered off the MCM-41-
plays an important role in enhancing the catalytic activity. We also 2N-Pd(OAc)2 complex after 2 h of reaction time and allowed the
compared the reactivity of the MCM-41-2N-Pd(OAc)2 with that of filtrate to react further. The catalyst filtration was performed at
some commercially available heterogeneous palladium cata- the reaction temperature (50 1C) in order to avoid possible
c
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Table 3 Heterogeneous coupling reaction of terminal alkynes with acyl chloridesa
Entry
R
R1
Time (h)
Product
Yieldb (%)
1
2
3
4
5
6
7
8
Ph
Ph
Ph
Ph
Ph
Ph
Ph
6
6
6
3
6
6
6
10
10
10
6
3
9
9
9
9
7
6
6
3a
3b
3c
3d
3e
3f
3g
3h
3i
3j
3k
3l
3m
3n
3o
3p
3q
3r
92
90
96
93
90
87
91
89
88
85
89
87
90
91
92
88
93
91
88
78
75
92
87
89
91
4-CH3C6H4
4-CH3OC6H4
4-ClC6H4
2-Furyl
2-Thienyl
Ph
4-CH3C6H4
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C6H13
n-C6H13
n-C6H13
n-C6H13
n-C6H13
n-C6H13
CH3OCH2
CH3OCH2
Me3Si
Me3Si
Me3Si
Me3Si
Ph
9
4-CH3C6H4
4-CH3OC6H4
4-ClC6H4
4-NO2C6H4
2-Furyl
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Ph
4-CH3C6H4
4-CH3OC6H4
4-ClC6H4
2-Furyl
2-Thienyl
Ph
4-CH3C6H4
Ph
4-CH3C6H4
4-CH3OC6H4
4-ClC6H4
3s
3t
3u
3v
3w
3x
3y
12
12
12
12
12
10
a
b
Reaction conditions: 1 (1.0 mmol), 2 (1.1 mmol), MCM-41-2N-Pd(OAc)2 (0.2 mol%), CuI (0.2 mol%) in Et3N (3.0 mL) at 50 1C under Ar. Isolated
yield.
recoordination or precipitation of soluble palladium upon cool- We also investigated the possibility to reuse the catalyst by
ing. We found that, after this hot filtration, no further reaction using the coupling reaction of 4-chlorobenzoyl chloride with
was observed. We also ascertained the Pd-content in the filtrate by phenylacetylene. After carrying out the reaction, the catalyst
ICP analysis, and only 0.2 ppm of palladium was found in the was separated by simple filtration and washed with 3 N HCl,
clear solution. This result suggests that the palladium catalyst EtOH, and Et2O. After being air-dried, it could be reused
remains on the support at elevated temperatures during the directly without further purification. The recovered palladium
reaction and points to a process of heterogeneous nature.
catalyst was used in the next run under identical conditions,
For a heterogeneous transition-metal catalyst, it is impor- and almost consistent activity was observed for ten consecutive
tant to examine its ease of separation, good of recoverability cycles (Table 4, entries 1–10). Fig. 1 shows the time course of
and reusability. This heterogeneous palladium catalyst can be the coupling reaction of 4-chlorobenzoyl chloride with phenyl-
easily recovered by a simple filtration of the reaction solution. acetylene using the fresh and the fourth recycled catalysts. As
Table 4 Coupling reaction of 4-chlorobenzoyl chloride with phenylacetylene catalyzed by the recycled catalysta
Cycle
Yieldb (%)
Cycle
Yieldb (%)
1
3
5
7
9
93
92
91
91
89
2
4
6
8
10
93
92
92
90
90
a
Reaction conditions: phenylacetylene (1.0 mmol), 4-chlorobenzoyl chloride (1.1 mmol), MCM-41-2N-Pd(OAc)2 (0.2 mol%), CuI (0.2 mol%) in Et3N
b
(3.0 mL) at 50 1C for 3 h under Ar. Isolated yield.
c
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Conclusion
In summary, we have developed a novel, phosphine-free, prac-
tical and economic catalyst system for the coupling reaction of
terminal alkynes with acyl chlorides by using an MCM-41-
immobilized bidentate nitrogen palladium complex as a cata-
lyst in Et3N. This novel heterogeneous palladium catalyst can
be very conveniently prepared by a simple two-step procedure
from commercially available and cheap reagents and recycled
by a simple filtration of the reaction solution and used for at
least 10 consecutive trials without any decrease in activity. The
heterogeneous coupling reaction of terminal alkynes with acyl
chlorides catalyzed by the MCM-41-2N-Pd(OAc)2 complex pro-
vides a better and practical procedure for the synthesis of a
variety of ynone compounds.
Fig. 1 Plot of GC yield versus time for the coupling reaction of 4-chlorobenzoyl
chloride with phenylacetylene using the fresh and the fourth recycled catalysts.
Experimental
General comments
Table 5 Textural parameters of the fresh and the 10th recycled catalysts
All chemicals were reagent grade and used as purchased. All
solvents were dried and distilled before use. The products were
purified by flash chromatography on silica gel. A mixture of
EtOAc and hexane was generally used as the eluent. All cou-
pling products were characterized by comparison of their
spectra and physical data with authentic samples. IR spectra
Surface areaa/
Pore volumeb/
Diameterc/
(nm)
Palladium catalyst
(m2 gꢀ1
)
(cm3 gꢀ1
)
Fresh catalyst
10th recycled catalyst
577.3
575.6
0.46
0.45
2.1
2.0
a
b
c
BET surface area. Single point total pore volume. Pore diameter
according to the maximum of the BJH pore size distribution.
1
were determined on a Perkin-Elmer 683 instrument. H NMR
spectra were recorded on a Bruker Avance 400 MHz spectro-
meter with TMS as an internal standard in CDCl3 as the solvent.
13C NMR spectra (100 MHz) were recorded on a Bruker Avance
400 MHz spectrometer in CDCl3 as solvent. The palladium
content was determined using inductively coupled plasma atom
emission Atomscan16 (ICP-AES, TJA Corporation). The BET sur-
face area and pore analysis were performed on an ASAP2010
(micromeritics) by N2 physical adsorption–desorption at 77.4 K.
The X-ray powder diffraction data were obtained on a Damx-rA
(Rigaka). X-ray photoelectron spectra were recorded on XSAM
800 (Kratos). Microanalyses were carried out using a Yanaco
MT-3 CHN microelemental analyzer. GC analysis was per-
formed on an SRI 8610C equipped with a fused silica capillary
column. The mesoporous material MCM-41 was easily prepared
according to a literature procedure.18
shown in Fig. 1, for the fourth recycled catalyst, the induction
period and the reaction rate in the fourth run did not change
significantly compared with that of the fresh one indicating the
excellent stability and recyclability of the catalytic system. In
addition, palladium leaching in the supported catalyst was also
determined. The palladium content of the recycled catalyst
was determined by ICP analysis to be 0.27 mmol gꢀ1 after ten
consecutive runs, and no palladium had been lost from
the MCM-41 support. By comparing the data on the porosity
of the fresh and the 10th recycled catalysts (Table 5), it is clear
that the mesoporous structure of MCM-41 remains intact
during the reaction procedure, indicating that MCM-41 is a
very stable material in dry Et3N medium.
From a mechanistic point of view, the Pd(II) will be reduced
to Pd(0) first and then a oxidative addition, transmetallation,
reductive elimination pathway could be the possible mechanism.
Preparation of MCM-41-2N
So, the structure of the recycled catalyst should be (N4N)2Pd(0). A solution of 1.54 g of 3-(2-aminoethylamino)propyltrimeth-
In general, the continuous recycle of resin-supported palladium oxysilane in 18 mL of dry chloroform was added to a suspension
catalysts is difficult owing to leaching of the palladium species from of 2.2 g of the MCM-41 in 180 mL of dry toluene. The mixture
the polymer supports, which often reduces their activity within a was stirred for 24 h at 100 1C. Then the solid was filtered and
five-recycle run. The high stability and excellent reusability of the washed with CHCl3 (2 ꢂ 20 mL), and dried under vacuum at
catalyst should result from the chelating action of the bidentate 160 1C for 5 h. The dried white solid was then soaked in a
2-aminoethylamino ligand on palladium and the mesoporous struc- solution of 3.1 g of Me3SiCl in 100 mL of dry toluene at room
ture of the MCM-41 support. The result is important from a practical temperature under stirring for 24 h. Then the solid was filtered,
point of view. The high catalytic activity, excellent reusability and the washed with acetone (3 ꢂ 20 mL) and diethyl ether (3 ꢂ 20 mL),
easy accessibility of the MCM-41-2N-Pd(OAc)2 complex make it a and dried under vacuum at 120 1C for 5 h to obtain 3.49 g of
highly attractive heterogeneous palladium catalyst for the parallel hybrid material MCM-41-2N. The nitrogen content was found to
solution phase synthesis of diverse libraries of compounds.
be 1.84 mmol gꢀ1 by elemental analysis.
c
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Preparation of MCM-41-2N-Pd(OAc)2
(m, 4H), 6.61 (t, J = 1.8 Hz, 1H). 13C NMR (100 MHz, CDCl3)
d (ppm): 164.8, 153.3, 148.0, 133.1, 130.9, 128.7, 120.9, 120.0,
112.7, 91.9, 86.3.
In a small Schlenk tube, 2.03 g of the above-functionalized
MCM-41 (MCM-41-2N) was mixed with 0.137 g (0.61 mmol) of
Pd(OAc)2 in 50 mL of dry acetone. The mixture was refluxed for
72 h under an argon atmosphere. The solid product was filtered
by suction, washed with acetone, distilled water and acetone
successively and dried at 70 1C/26.7 Pa under Ar for 5 h to give
2.12 g of a light yellow palladium complex [MCM-41-2N-
Pd(OAc)2]. The nitrogen and palladium contents were found
to be 1.68 mmol gꢀ1 and 0.27 mmol gꢀ1, respectively.
3-Phenyl-1-(thiophen-2-yl)propynone 3f [Table 3, entry 6]14
.
Brown solid, mp 54–55 1C. IR (KBr): nmax/cmꢀ1 2199, 1725,
1614, 1489, 1410, 1359, 1308, 1230, 1082, 1053, 966, 758, 725.
1H NMR (400 MHz, CDCl3) d (ppm): 8.01 (d, J = 4.0 Hz, 1H), 7.73
(d, J = 4.8 Hz, 1H), 7.67 (d, J = 8.4 Hz, 2H), 7.51–7.40 (m, 3H),
7.19 (t, J = 4.2 Hz, 1H). 13C NMR (100 MHz, CDCl3) d (ppm):
169.8, 145.0, 135.2, 135.0, 133.1, 130.9, 128.7, 128.3, 120.0,
91.7, 86.5.
1-Phenyl-3-(4-methylphenyl)propynone 3g [Table 3, entry 7]14.
White solid, mp 66–67 1C. IR (KBr): nmax/cmꢀ1 2194, 1629, 1604,
General procedure for the synthesis of ynones
An oven-dried Schlenk tube equipped with a magnetic stirring 1316, 1295, 1209, 1009, 816, 697. 1H NMR (400 MHz, CDCl3)
bar was charged with MCM-41-2N-Pd(OAc)2 (8 mg, 0.002 mmol d (ppm): 8.22 (d, J = 8.4 Hz, 2H), 7.69–7.49 (m, 5H), 7.23
Pd), aromatic acyl chloride (1.1 mmol), and terminal alkyne (d, J = 8.0 Hz, 2H), 2.41 (s, 3H). 13C NMR (100 MHz, CDCl3)
(1.0 mmol) followed by anhydrous Et3N (3 mL) under Ar. The d (ppm): 178.1, 141.6, 137.0, 134.0, 133.1, 129.6, 129.5, 128.6,
reaction mixture was stirred in an oil bath at 50 1C for 3–12 h. 117.0, 93.8, 86.8, 21.8.
The mixture was cooled to room temperature, diluted with
1-Phenylhept-2-yn-1-one 3h [Table 3, entry 8]6. Pale yellow
diethyl ether (30 mL) and filtered. The MCM-41-2N-Pd(OAc)2 oil. IR (film): nmax/cmꢀ1 2959, 2201, 1643, 1597, 1449, 1313,
1
complex was washed with 3 N HCl (2 ꢂ 5 mL), EtOH (2 ꢂ 5 mL), 1267, 1175, 911, 702. H NMR (400 MHz, CDCl3) d (ppm): 8.14
and Et2O (2 ꢂ 5 mL) and reused in the next run. The filtrate was (d, J = 8.0 Hz, 2H), 7.60 (t, J = 7.2 Hz, 1H), 7.50–7.45 (m, 2H),
washed with water (2 ꢂ 10 mL) and dried over anhydrous 2.51 (t, J = 6.8 Hz, 2H), 1.69–1.61 (m, 2H), 1.54–1.48 (m, 2H),
magnesium sulfate. The solvent was removed and the residue 0.97 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) d (ppm):
was purified by flash column chromatography on silica gel 178.3, 136.9, 133.9, 129.6, 128.5, 96.9, 79.7, 29.9, 22.1,
(hexane–ethyl acetate = 10 : 1).
18.9, 13.6.
1-(4-Methylphenyl)hept-2-yn-1-one 3i [Table 3, entry 9]6. Pale
1,3-Diphenylpropynone 3a [Table 3, entry 1]3a. White solid,
mp 43–44 1C. IR (KBr): nmax/cmꢀ1 2203, 1636, 1603, 1288, 1013, yellow oil. IR (film): nmax/cmꢀ1 2959, 2199, 1643, 1605, 1269,
761. 1H NMR (400 MHz, CDCl3) d (ppm): 8.23 (d, J = 7.6 Hz, 2H), 1177, 910, 742. 1H NMR (400 MHz, CDCl3) d (ppm): 8.03 (d, J =
7.70 (d, J = 7.2 Hz, 2H), 7.64 (t, J = 7.2 Hz, 1H), 7.55–7.41 8.0 Hz, 2H), 7.27 (d, J = 8.0 Hz, 2H), 2.50 (t, J = 7.2 Hz, 2H), 2.43
(m, 5H). 13C NMR (100 MHz, CDCl3) d (ppm): 178.1, 136.9, (s, 3H), 1.70–1.64 (m, 2H), 1.53–1.47 (m, 2H), 0.96 (t, J = 7.4 Hz,
134.2, 133.1, 130.9, 129.6, 128.7, 128.6, 120.1, 93.2, 86.9.
3H). 13C NMR (100 MHz, CDCl3) d (ppm): 178.0, 144.9, 134.6,
1-(4-Methylphenyl)-3-phenylpropynone 3b [Table 3, entry 2]19. 129.7, 129.2, 96.3, 79.7, 29.9, 22.1, 21.8, 18.9, 13.6.
White solid, mp 86–87 1C. IR (KBr): nmax/cmꢀ1 2198, 1636, 1604,
1-(4-Methoxyphenyl)hept-2-yn-1-one 3j [Table 3, entry 10]6.
1
1288, 1211, 1013, 761, 690. H NMR (400 MHz, CDCl3) d (ppm): Pale yellow oil. IR (film): nmax/cmꢀ1 2959, 2201, 1639, 1599,
8.12 (d, J = 8.0 Hz, 2H), 7.68 (d, J = 8.0 Hz, 2H), 7.48 (t, J = 6.8 Hz, 1508, 1317, 1259, 1167, 1029, 911, 845, 759. 1H NMR (400 MHz,
1H), 7.42 (t, J = 7.2 Hz, 2H), 7.31 (d, J = 7.6 Hz, 2H), 2.45 (s, 3H). CDCl3) d (ppm): 8.11 (d, J = 8.0 Hz, 2H), 6.95 (d, J = 8.0 Hz, 2H),
13C NMR (100 MHz, CDCl3) d (ppm): 177.7, 145.2, 134.7, 133.0, 3.89 (s, 3H), 2.50 (t, J = 6.6 Hz, 2H), 1.68–1.64 (m, 2H), 1.54–1.48
130.7, 129.7, 129.4, 128.7, 120.3, 92.6, 87.0, 21.8.
(m, 2H), 0.96 (t, J = 6.8 Hz, 3H). 13C NMR (100 MHz, CDCl3)
1-(4-Methoxyphenyl)-3-phenylpropynone 3c [Table 3, entry 3]3a. d (ppm): 177.1, 164.3, 132.0, 130.3, 113.7, 96.0, 79.6, 55.6, 29.9,
White solid, mp 98–99 1C. IR (KBr): nmax/cmꢀ1 2201, 1634, 1602, 22.1, 18.9, 13.6.
1316, 1210, 1014, 762, 693. 1H NMR (400 MHz, CDCl3)
1-(4-Chlorophenyl)hept-2-yn-1-one 3k [Table 3, entry 11]6.
d (ppm): 8.21 (d, J = 8.0 Hz, 2H), 7.69 (d, J = 7.2 Hz, 2H), 7.49 Pale yellow oil. IR (film): nmax/cmꢀ1 2961, 2201, 1650, 1587,
(t, J = 6.8 Hz, 1H), 7.43 (t, J = 7.2 Hz, 2H), 7.00 (d, J = 8.0 Hz, 2H), 1485, 1401, 1264, 1171, 1091, 911, 847, 748. 1H NMR (400 MHz,
3.91 (s, 3H). 13C NMR (100 MHz, CDCl3) d (ppm): 176.7, 164.5, CDCl3) d (ppm): 8.07 (d, J = 8.4 Hz, 2H), 7.46 (d, J = 8.4 Hz, 2H),
133.0, 132.0, 130.6, 130.3, 128.7, 120.4, 113.9, 92.4, 87.2, 55.6.
2.52 (t, J = 7.2 Hz, 2H), 1.69–1.63 (m, 2H), 1.53–1.46 (m, 2H),
1-(4-Chlorophenyl)-3-phenylpropynone 3d [Table 3, entry 4]3a. 0.97 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) d (ppm):
White solid, mp 106–107 1C. IR (KBr): nmax/cmꢀ1 2200, 1654, 177.0, 140.5, 135.3, 131.0, 128.9, 97.5, 79.4, 29.8, 22.1,
1585, 1303, 1207, 1170, 1091, 752, 682. 1H NMR (400 MHz, 18.9, 13.6.
CDCl3) d (ppm): 8.17 (d, J = 7.6 Hz, 2H), 7.69 (d, J = 8.0 Hz, 2H),
1-(4-Nitrophenyl)hept-2-yn-1-one 3l [Table 3, entry 12]6. Yellow
7.51–7.44 (m, 5H). 13C NMR (100 MHz, CDCl3) d (ppm): 176.7, oil. IR (film): nmax/cmꢀ1 2960, 2201, 1653, 1603, 1528, 1344, 1320,
1
140.8, 135.3, 133.1, 131.0, 130.9, 129.0, 128.8, 119.9, 93.7, 86.6.
1261, 1105, 912, 850, 711. H NMR (400 MHz, CDCl3) d (ppm):
8.33 (d, J = 8.8 Hz, 2H), 8.29 (d, J = 8.8 Hz, 2H), 2.55 (t, J = 7.2 Hz,
1-(Furan-2-yl)-3-phenylpropynone 3e [Table 3, entry 5]3a
.
Brown solid, mp 49–50 1C. IR (KBr): nmax/cmꢀ1 2201, 1713, 1634, 2H), 1.72–1.66 (m, 2H), 1.55–1.48 (m, 2H), 0.98 (t, J = 7.2 Hz, 3H).
1567, 1463, 1395, 1312, 1161, 1043, 1008, 758, 689. 1H NMR 13C NMR (100 MHz, CDCl3) d (ppm): 176.1, 150.8, 141.1, 130.4,
(400 MHz, CDCl3) d (ppm): 7.70–7.64 (m, 3H), 7.52–7.41 123.8, 99.5, 79.4, 29.7, 22.1, 19.0, 13.5.
c
3142 New J. Chem., 2013, 37, 3137--3144
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NJC
1-(Furan-2-yl)hept-2-yn-1-one 3m [Table 3, entry 13]19. Pale
Paper
4-Methoxy-1-phenylbut-2-yn-1-one 3t [Table 3, entry 20]22
.
yellow oil. IR (film): nmax/cmꢀ1 2960, 2210, 1635, 1566, 1463, Pale yellow oil. IR (film): nmax/cmꢀ1 2934, 2227, 1723, 1651,
1394, 1302, 1171, 1124, 1017, 884, 827, 765. 1H NMR (400 MHz, 1598, 1450, 1314, 1263, 1175, 1105, 701. 1H NMR (400 MHz,
CDCl3) d (ppm): 7.64 (d, J = 0.8 Hz, 1H), 7.31 (d, J = 3.2 Hz, 1H), CDCl3) d (ppm): 8.15 (d, J = 7.6 Hz, 2H), 7.64 (t, J = 7.4 Hz, 1H),
6.57–6.55 (m, 1H), 2.47 (t, J = 7.0 Hz, 2H), 1.66–1.58 (m, 2H), 7.51 (t, J = 7.6 Hz, 2H), 4.41 (s, 2H), 3.51 (s, 3H). 13C NMR
1.52–1.46 (m, 2H), 0.96 (t, J = 7.4 Hz, 3H). 13C NMR (100 MHz, (100 MHz, CDCl3) d (ppm): 177.5, 136.3, 134.4, 129.6, 128.7,
CDCl3) d (ppm): 165.1, 153.3, 147.7, 120.5, 112.5, 95.6, 79.0, 90.0, 84.2, 59.8, 58.3.
29.7, 22.0, 18.8, 13.5.
4-Methoxy-1-(p-tolyl)but-2-yn-1-one 3u [Table 3, entry 21].
1-Phenylnon-2-yn-1-one 3n [Table 3, entry 14]14. Pale yellow Pale yellow oil. IR (film): nmax/cmꢀ1 2928, 2227, 1645, 1605,
oil. IR (film): nmax/cmꢀ1 2931, 2201, 1646, 1598, 1450, 1313, 1450, 1310, 1266, 1178, 1105, 740. H NMR (400 MHz, CDCl3)
1265, 1175, 909, 702. H NMR (400 MHz, CDCl3) d (ppm): 8.14 d (ppm): 8.04 (d, J = 8.4 Hz, 2H), 7.29 (d, J = 8.4 Hz, 2H), 4.39
1
1
(d, J = 8.0 Hz, 2H), 7.59 (t, J = 7.4 Hz, 1H), 7.47 (t, J = 7.6 Hz, 2H), (s, 2H), 3.50 (s, 3H), 2.44 (s, 3H). 13C NMR (100 MHz, CDCl3)
2.50 (t, J = 7.2 Hz, 2H), 1.72–1.64 (m, 2H), 1.52–1.33 (m, 6H), d (ppm): 177.2, 145.5, 134.1, 129.8, 129.4, 89.4, 84.4, 59.8, 58.2,
0.91 (t, J = 6.8 Hz, 3H). 13C NMR (100 MHz, CDCl3) d (ppm): 21.9. Anal. calcd for C12H12O2: C, 76.57; H, 6.43. Found: C,
178.2, 137.0, 133.8, 129.5, 128.5, 96.9, 79.7, 31.2, 28.6, 27.8, 76.34; H, 6.64.
22.5, 19.2, 14.0.
1-Phenyl-3-(trimethylsilyl)propynone 3v [Table 3, entry 22]23
.
1-(4-Methylphenyl)non-2-yn-1-one 3o [Table 3, entry 15]20
.
Pale yellow oil. IR (film): nmax/cmꢀ1 2963, 2153, 1645, 1598,
Pale yellow oil. IR (film): nmax/cmꢀ1 2931, 2199, 1645, 1605, 1254, 1036, 1018, 848, 701. 1H NMR (400 MHz, CDCl3) d (ppm):
1
1465, 1309, 1268, 1176, 1107, 741. H NMR (400 MHz, CDCl3) 8.15 (d, J = 7.6 Hz, 2H), 7.65 (t, J = 7.6 Hz, 1H), 7.48 (t, J = 7.6 Hz,
d (ppm): 8.03 (d, J = 8.0 Hz, 2H), 7.27 (d, J = 8.0 Hz, 2H), 2.49 (t, J = 2H), 0.33 (s, 9H). 13C NMR (100 MHz, CDCl3) d (ppm): 177.8,
7.2 Hz, 2H), 2.43 (s, 3H), 1.69–1.64 (m, 2H), 1.51–1.33 (m, 6H), 136.5, 134.2, 129.7, 128.6, 100.8, 100.6, ꢀ0.7.
0.91 (t, J = 6.8 Hz, 3H). 13C NMR (100 MHz, CDCl3) d (ppm):
1-(4-Methylphenyl)-3-(trimethylsilyl)propynone 3w [Table 3,
177.9, 144.8, 134.7, 129.7, 129.2, 96.3, 79.8, 31.2, 28.6, 27.8, 22.5, entry 23]. Pale yellow oil. IR (film): nmax/cmꢀ1 2962, 2154, 1644,
21.7, 19.2, 14.0.
1605, 1259, 1175, 1036, 1016, 848, 741. 1H NMR (400 MHz,
CDCl3) d (ppm): 8.04 (d, J = 8.4 Hz, 2H), 7.28 (t, J = 8.4 Hz, 2H),
1-(4-Methoxyphenyl)non-2-yn-1-one 3p [Table 3, entry 16]20
.
Pale yellow oil. IR (film): nmax/cmꢀ1 2933, 2200, 1643, 1599, 2.44 (s, 3H), 0.32 (s, 9H). 13C NMR (100 MHz, CDCl3) d (ppm):
1464, 1316, 1257, 1167, 1029, 845, 759. 1H NMR (400 MHz, 178.1, 146.0, 134.9, 130.5, 130.0, 101.6, 100.6, 22.5, 0.0. Anal.
CDCl3) d (ppm): 8.11 (d, J = 8.8 Hz, 2H), 6.94 (d, J = 8.8 Hz, 2H), calcd for C13H16OSi: C, 72.20; H, 7.46. Found: C, 72.32; H, 7.29.
3.89 (s, 3H), 2.48 (t, J = 7.2 Hz, 2H), 1.69–1.63 (m, 2H), 1.49–1.32
1-(4-Methoxyphenyl)-3-(trimethylsilyl)propynone 3x [Table 3,
(m, 6H), 0.91 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) entry 24]23. Pale yellow oil. IR (film): nmax/cmꢀ1 2961, 2252,
d (ppm): 177.0, 164.3, 131.9, 130.4, 113.7, 96.0, 79.6, 55.6, 31.3, 1637, 1598, 1257, 1165, 1026, 910, 846, 734. 1H NMR (400 MHz,
28.7, 27.8, 22.5, 19.2, 14.1.
CDCl3) d (ppm): 8.12 (d, J = 8.8 Hz, 2H), 6.96 (d, J = 8.8 Hz, 2H),
1-(4-Chlorophenyl)non-2-yn-1-one 3q [Table 3, entry 17]. Pale 3.89 (s, 3H), 0.31 (s, 9H). 13C NMR (100 MHz, CDCl3) d (ppm):
yellow oil. IR (film): nmax/cmꢀ1 2931, 2201, 1649, 1587, 1263, 177.0, 165.2, 132.7, 130.6, 114.5, 102.1, 100.2, 56.2, 0.0.
1
1091, 1014, 846, 747. H NMR (400 MHz, CDCl3) d (ppm): 8.07
1-(4-Chlorophenyl)-3-(trimethylsilyl)propynone 3y [Table 3,
(d, J = 8.4 Hz, 2H), 7.44 (d, J = 8.4 Hz, 2H), 2.50 (t, J = 7.2 Hz, 2H), entry 25]. Pale yellow oil. IR (film): nmax/cmꢀ1 2963, 2155, 1651,
1.69–1.63 (m, 2H), 1.49–1.31 (m, 6H), 0.91 (t, J = 6.8 Hz, 3H). 13 1587, 1252, 1170, 1092, 1034, 846, 747. 1H NMR (400 MHz,
C
NMR (100 MHz, CDCl3) d (ppm): 176.8, 140.4, 135.4, 130.9, CDCl3) d (ppm): 8.08 (d, J = 8.4 Hz, 2H), 7.47 (t, J = 8.4 Hz, 2H),
128.8, 97.4, 79.4, 31.2, 28.6, 27.7, 22.5, 19.2, 14.0. Anal. calcd for 0.32 (s, 9H). 13C NMR (100 MHz, CDCl3) d (ppm): 177.1, 141.5,
C
15H17OCl: C, 72.41; H, 6.89. Found: C, 72.18; H, 6.64.
135.6, 131.7, 129.7, 102.0, 101.1, 0.0. Anal. calcd for C12H13OS-
1-(Furan-2-yl)non-2-yn-1-one 3r [Table 3, entry 18]21. Pale iCl: C, 60.88; H, 5.54. Found: C, 60.62; H, 5.31.
yellow oil. IR (film): nmax/cmꢀ1 2931, 2210, 1634, 1566, 1463,
1395, 1302, 1171, 1016, 765. 1H NMR (400 MHz, CDCl3)
d (ppm): 7.64 (s, 1H), 7.31 (d, J = 3.6 Hz, 1H), 6.57–6.55 (m, 1H),
2.46 (t, J = 7.0 Hz, 2H), 1.69–1.61 (m, 2H), 1.48–1.32 (m, 6H), 0.91
(t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) d (ppm): 165.1,
153.3, 147.7, 120.5, 112.4, 95.6, 79.0, 31.2, 28.6, 27.7, 22.5,
19.1, 14.0.
Acknowledgements
We thank the National Natural Science Foundation of China
(Project no. 20862008) and the Natural Science Foundation of
Jiangxi Province (Project no. 2010GZH0062).
1-(Thiophen-2-yl)non-2-yn-1-one 3s [Table 3, entry 19]21. Pale
yellow oil. IR (film): nmax/cmꢀ1 2931, 2230, 1629, 1515, 1411,
1358, 1279, 1041, 728. 1H NMR (400 MHz, CDCl3) d (ppm):
7.90–7.88 (m, 1H), 7.69–7.67 (m, 1H), 7.16–7.13 (m, 1H),
2.48 (t, J = 7.0 Hz, 2H), 1.68–1.61 (m, 2H), 1.49–1.26 (m, 6H),
0.91 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) d (ppm):
170.1, 145.1, 134.9, 134.8, 128.2, 95.5, 79.3, 31.2, 28.6, 27.7,
22.5, 19.1, 14.0.
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