Highly-efficient and recyclable nanosized MCM-41 anchored palladium bipyridyl complex-catalyzed coupling of acyl chlorides and terminal alkynes for the formation of ynones

Article abstract of DOI:10.1016/j.tet.2009.10.031

A highly-efficient and practical method for the formation of ynones from a variety of acyl chlorides and terminal alkynes catalyzed by a nanosized MCM-41 anchored palladium bipyridyl complex is described herein. Aroyl, heteroaroyl, and alkyl acyl chlorides were easily coupled with terminal alkynes, giving good to high isolated yields in the presence of a very low catalyst loading (0.002-0.1 mol % Pd) in Et₃N or diisopropylethylamine at 50 °C. Furthermore, the reaction scale was up to 150 mmol for a single batch reaction, providing the potential for practically synthetic application. After centrifugation, the supported catalyst was able to be recycled and reused several times with only a slight decrease in activity.

Full text of DOI:10.1016/j.tet.2009.10.031

Tetrahedron 65 (2009) 10134–10141
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Tetrahedron
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Highly-efficient and recyclable nanosized MCM-41 anchored palladium bipyridyl
complex-catalyzed coupling of acyl chlorides and terminal alkynes for the
formation of ynones
,
Jun-You Chen a, Tze-Chiao Lin a, Szu-Chien Chen a, Ai-Jan Chen b, Chung-Yuan Mou b, Fu-Yu Tsai a
*
a Institute of Organic and Polymeric Materials, National Taipei University of Technology, 1, Sec. 3, Chung-Hsiao E. Rd., Taipei 106, Taiwan
b Department of Chemistry, National Taiwan University, Taipei 106, Taiwan
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 30 July 2009
Received in revised form 2 October 2009
Accepted 9 October 2009
Available online 13 October 2009
A highly-efficient and practical method for the formation of ynones from a variety of acyl chlorides and
terminal alkynes catalyzed by a nanosized MCM-41 anchored palladium bipyridyl complex is described
herein. Aroyl, heteroaroyl, and alkyl acyl chlorides were easily coupled with terminal alkynes, giving
good to high isolated yields in the presence of a very low catalyst loading (0.002–0.1 mol % Pd) in Et3N or
diisopropylethylamine at 50 ꢀC. Furthermore, the reaction scale was up to 150 mmol for a single batch
reaction, providing the potential for practically synthetic application. After centrifugation, the supported
catalyst was able to be recycled and reused several times with only a slight decrease in activity.
Ó 2009 Elsevier Ltd. All rights reserved.
Keywords:
Palladium bipyridyl complex
Mesoporous silica
Recyclable catalyst
Acyl chloride
Ynone
1. Introduction
developments in ordered mesoporous silica (OMS) materials such
as MCM-41 and SBA-15 lend these materials very well to their use
Ynones are useful synthetic intermediates for the preparation
of many biologically-active compounds and heterocyclic de-
rivatives.1,2 Among many synthetic strategies, the coupling re-
action of acyl chlorides and terminal alkynes catalyzed by
palladium catalysts has received much attention of late. This
reaction can be achieved under mild conditions with a wide
range of functional groups on alkynes and enhanced chemo-
selectivity.3 In spite of the synthetic elegance of the construction
of synthetically useful ynones, these palladium-catalyzed re-
actions are usually carried out in a homogeneous phase, which
makes the catalysts difficult to recover and reuse in subsequent
reactions. Hence, facile separation of catalysts and products for
the recycling of the catalysts is rather important from the
viewpoints of economical and environmental concern. For these
reasons, heterogenization of such homogeneous catalysts used
for ynone formation is very valuable.
as solid supports for the purpose of heterogenization of homoge-
neous catalysts.5 The uniform pore size and large surface area of
OMS allow simple grafting of transition-metal complexes to
the wall and the catalysis of organic reactions in the nanopores.
Recently, several palladium complexes have been immobilized on
OMS for employment as heterogeneous catalysts for carbon–car-
bon bond-forming reactions, such as the Mizoroki–Heck reaction,6
Suzuki–Miyaura reaction,7 Sonogashira coupling,8 Kumada–
Tamao–Corriu reaction,9 Migita–Kosugi–Stille reaction,10 and ke-
tone formation.11 We have reported previously that nanosized
MCM-41–Pd (Fig. 1) is an excellent heterogeneous catalyst for
carbon–carbon bond cross–coupling reactions due to its short and
highly-connected wormhole-like channels, which allow easy
exchange of reactants and products throughout the nano-
channels.6g,9,11 Thus, a very low catalyst loading can be used in the
reaction without encountering the saturation phenomenon. As
a part of our continuing efforts in the development of a recyclable
catalyst for carbon–carbon bond-forming reactions, we report
herein the coupling of various acyl chlorides and terminal alkynes
catalyzed by nanosized MCM-41–Pd (denoted as NS-MCM-41–Pd)
for the formation of ynones. This reaction not only uses a very low
catalyst loading (0.002–0.1 mol % Pd) in each batch, but also the
reaction scale can be up to 150 mmol, making it useful for practi-
cally synthetic application (Scheme 1).
Recently, Likhar’s group reported that acyl chlorides could be
coupled with terminal alkynes in the presence of 1 mol % Pd/C
under refluxing toluene and the catalyst could be reused for five
cycles with a 15% leaching of Pd.4 On the other hand, recent
* Corresponding author. Fax: þ886 2 2731 7174.
E-mail address: fuyutsai@ntut.edu.tw (F.-Y. Tsai).
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.10.031

J.-Y. Chen et al. / Tetrahedron 65 (2009) 10134–10141
10135
Nanosized MCM-41 wall
reaction system to obtain satisfactory results (entries 9–10). In order
to compare the activity of this heterogeneous catalyst, NS-MCM-41–
Pd, with a homogeneous one, PdCl2(bpy) was used as the catalyst for
the same reaction. Under identical conditions, a 66% yield of 3a was
isolated, indicating that higher catalytic activity was obtained after
heterogenization of the palladium catalyst as compared with the
homogeneous counterpart (entry 11).
O
Si
O
Si
O
O
O
O
NH
HN
After the optimized conditions had been found, a variety of acyl
chlorides were coupled with phenylacetylene (Table 2, the products
weredenoted as 3 when aromatic terminal alkynes were used). First,
we increased the ratio of phenylacetylene to Pd to 50 000 by scaling
up the alkyne to 150 mmol. To our delight, the reaction was com-
pleted in 36 h and resulted in a 93% isolated yield (entry 1). This
result shows its potential for practically synthetic application. Not
only aryl acyl chlorides but also heteroaryl chlorides coupled with
phenylacetylene smoothly in the presence of low amount of NS-
MCM-41–Pd within a short reaction time to give high product yields
when both aroyl and heteroaroyl chlorides were used as the sub-
strates (entries 2–7). Under similar conditions, we also studied the
reactivity of alkyl acyl chlorides in the presence of 0.02 mol % of the
Pd catalyst: 1h–1j coupled with phenacetylene effectively, resulting
in the formation of the corresponding products at yields of between
86 and 94% (entries 8–10). In the case of valeroyl chloride,1k, a bulky
diisopropylethylamine was employed instead of Et3N to avoid direct
reaction of the amine with the linear aliphatic acyl chloride,3f,12
whereupon a good isolated yield of 3k was obtained (entry 11).
Next, a variety of substituted aromatic terminal alkynes were
used to couple with acyl chlorides in the presence of 0.02 mol %
NS-MCM-41–Pd (Table 3). The para-substituted phenylacetylenes,
such as 4-ethynylanisole 2b and 4-ethynylchlorobenzene 2c, reac-
ted with various aroyl and alkyl acyl chlorides very efficiently,
giving the corresponding products, 3l–3s, in high yields within
short reaction time (entries 1–8). Terminal alkynes 2d–2h also
coupled with acyl chlorides smoothly under the same conditions
(entries 9–19), and even reaction with ortho-substituted alkynes
2d, 2e, and 2h proceeded with yields almost at the same level as the
para-substituted alkynes (entries 9–11). However, the reaction rate
when employing the larger 9-ethynylphenanthrene 2i was smaller
owing to the difficulty of diffusion of the bulky reactant in the
catalyst-containing nanopores (entry 20).
N
N
Pd
Cl
Cl
Figure 1. Nanosized MCM-41–Pd.
O
O
NS-MCM-41-Pd
+
R'
R
Cl
R
CuI, PPh , Et N, 50 °C
R'
3
3
R = aryl, heteroaryl, alkyl
R' = aryl, alkyl, alkenyl
Scheme 1. NS-MCM-41–Pd-catalyzed coupling of acyl chlorides with terminal alkynes.
2. Results and discussion
NS-MCM-41–Pd was prepared according to our previous proce-
dures.6g,9 After the grafting of the palladium bipyridyl complex onto
NS-MCM-41, the surface area and pore diameter decreased from
705 m2/g and 2.5 nm to 588 m2/g and 2.3 nm, respectively, and the
amount of Pd complex anchored on the wall of MCM-41 was esti-
mated to be 0.15 mmol/g by ICP-MASS analysis. As shown in Table 1,
our initial goal was to optimize the reaction conditions for the
coupling of benzoyl chloride 1a (1.3 equiv) and phenylacetylene 2a
(1.0 equiv) in the presence of 0.02 mol % Pd (as in NS-MCM-41–Pd).
When the reaction was conducted in common organic solvents such
as THF, toluene, DME, and 1,4-dioxane with Et3N as a base, low GC
yields were obtained (entries 1–4). The coupling reaction was
completely blocked as inorganic bases such as KOH and K2CO3 were
employed, presumably owing to the poor solubility of these salts in
organic solvents (entries 5–6). When Et3N was used as both solvent
and base, the reaction showed high activity and afforded near-
quantitative yield at 50 ꢀC in 0.5 h (entry 7). However, only a 10%
yield of 3a was obtained when the reaction was conducted at room
temperature (entry 8), and both PPh3 and CuI had to be added to the
The utility of this coupling reaction for aliphatic terminal
alkynes was also evaluated (Table 4, the products were denoted as 4
when aliphatic terminal alkynes were used). Compared with that
of aromatic terminal alkynes, the coupling of acyl chlorides with
aliphatic terminal alkynes proceeded at relatively lower rates.
When a higher catalyst loading (0.1 mol %) was applied, however,
both aroyl and alkyl acyl chlorides coupled with aliphatic terminal
alkynes to give the corresponding products 4a–4i in good to high
yields (entries 1–9).
Table 1
Optimization of reaction conditions for the coupling of benzoyl chloride 1a with
phenylacetylene 2aa
In order to determine whether catalysis was due to NS-MCM-
41–Pd itself or to the leached palladium in solution, a hot filtration
experiment was performed.6–11 We performed a coupling reaction
of 4-methoxybenzoyl chloride 1b and phenylacetylene 2a cata-
lyzed by 0.01 mol % of NS-MCM-41–Pd (Table 2, entry 2). After 1 h
of reaction, the reaction mixture was promptly filtered through
a dried Celite pad under nitrogen at the reaction temperature to
remove any undissolved fine particles. The clear filtrate was
analyzed by GC and a yield of 53% was obtained; the solution was
then stirred at 50 ꢀC, and we observed that the clear filtrate showed
no further activity for the coupling reaction, even upon stirring for
an additional 12 h. We ascertained the Pd-content in the filtrate by
ICP-MASS, and only 0.3 ppm of palladium was found in the clear
solution. This indicated that the catalytic activity indeed was
resulted from the grafted palladium complex.
Entry
Base
Solvent
Temperature (ꢀC)
Yieldb (%)
1
2
3
4
5
6
7
8
Et3N
Et3N
Et3N
Et3N
K2CO3
KOH
Et3N
Et3N
Et3N
Et3N
Et3N
THF
Toluene
DME
1,4-Dioxane
THF
THF
Et3N
Et3N
Et3N
Et3N
50
50
50
50
50
50
50
rt
21
14
3
21
0
0
99 (92)
10
2
7
9c
10d
11e
50
50
50
Et3N
78 (66)
a
Reaction conditions: benzoyl chloride (19.5 mmol), phenylacetylene (15 mmol),
NS-MCM-41–Pd (0.02 mol %), PPh3 (0.04 mol %), CuI (0.04 mol %), base (30 mmol),
and solvent (20 mL) for 0.5 h.
b
GC yields. Isolated yields are shown in parentheses.
Without PPh3.
Without CuI.
PdCl2(bpy) was used as the catalyst.
c
d
One of the purposes for the designing of this heterogeneous
catalyst is to enable recycling of the catalyst for use in subsequent
e

10136
J.-Y. Chen et al. / Tetrahedron 65 (2009) 10134–10141
Table 2
NS-MCM-41–Pd-catalyzed coupling of acyl chlorides 1 with phenylacetylene 2aa
Entry
1c
Acyl chloride
[Pd] (mol %)
Time (h)
36
Product
Yieldb (%)
93
O
O
0.002
Cl
1a
3a
3b
Ph
O
O
2
3
0.01
0.01
6
6
96
85
Cl
Ph
1b
1c
MeO
MeO
O
O
Cl
3c
Ph
O
O
4
5
0.01
0.02
6
1
87
77
Cl
1d
3d
3e
Ph
O
O
Cl
Ph
1e
Cl
O
Cl
O
O
O
6
7
0.02
0.02
6
6
90
88
Cl
O
3f
1f
Ph
O
O
S
S
Cl
3g
3h
1g
1h
Ph
Ph
O
8
9
0.02
0.02
0.5
1
94
86
Cl
O
O
Cl
1i
Ph
3i
O
O
10
0.02
9
86
58
Cl
1j
Ph
3j
O
O
11d
0.1
24
Cl
1k
Ph
3k
a
Reaction conditions: in Et3N at 50 ꢀC. [acyl chloride]:[phenylacetylene]¼1.3:1. [NS-MCM-41–Pd]:[PPh3]:[CuI]¼1:2:2.
b
c
Isolated yields.
150 mmol of phenylacetylene was used.
Diisopropylethylamine was used as both base and solvent.
d
reactions. For the recycle experiment, we used cyclohexanecarbonyl
The catalyst can be easily recycled by centrifugation and reused
several times with only a slight decrease in activity. Furthermore,
this method involves reactants on a large scale (up to 150 mmol)
with a very low catalyst loading (0.002–0.1 mol % Pd), rendering it
suitable for practically synthetic application of very high yield. Fur-
ther studies are in progress to develop new carbon–carbon bond-
forming reactions catalyzed with this recyclable catalytic system.
chloride 1h and phenylacetylene 2a as the representative reactants
in the presence of 0.1 mol % NS-MCM-41–Pd to study the recycla-
bilityof this heterogeneous catalyst (see Section 4.3). Aftera reaction
time of 0.5 h at 50 ꢀC, the mixture from the first-run reaction was
centrifuged and the solid obtained was washed alternately with 3 N
HCl and THF twice. After drying under vacuum, the recovered
NS-MCM-41–Pd was then re-used in the same reaction under
identical conditions. We found that the product yield decreased
slightly from 98 to 90% over four recycling runs (Scheme 2). This
slight decrease in the activity of NS-MCM-41–Pd indicated a high
stability uponworkup and excellent recyclability of this mesoporous
supported catalyst. After our analysis of this recovered catalyst by
ICP-MASS, the amount of Pd in the catalyst is still 0.15 mmol/g. The
slight decrease of activity is presumably due to the gradual
deactivation of the catalyst in the nanopores.
4. Experimental
4.1. General
All reactions involving air- and moisture-sensitive conditions
were carried out in a dry nitrogen atmosphere. The chemicals were
purchased from commercial suppliers and were used without fur-
ther purification. THF, 1,4-dioxane, DME, and toluene were distilled
from sodium benzophenone ketyl. Et3N and diisopropylethylamine
were dried over KOH and then distilled. 4,40-Bis(bromomethyl)-
2,20-bipyridine,13 PdCl2(PhCN)2,14 and nanosized MCM-4115 were
prepared according to known procedures. The detailed procedure
for the preparation of NS-MCM-41–Pd was reported in our pre-
viously published paper.6g,9 Melting points were recorded using
3. Conclusion
In conclusion, we have shown that NS-MCM-41–Pd is a highly-
efficient and recyclable catalyst for the coupling of a variety of acyl
chlorides and terminal alkynes leading to the formation of ynones.

J.-Y. Chen et al. / Tetrahedron 65 (2009) 10134–10141
10137
Table 3
NS-MCM-41–Pd-catalyzed coupling of acyl chlorides with aromatic terminal alkynesa
Entry
Acyl chloride
Alkyne
[Pd] (mol %)
Time (h)
Product
Yieldb (%)
O
O
1
OMe
0.02
3
90
Cl
2b
1a
1b
1c
3l
O
OMe
O
2
3
2b
2b
0.02
0.02
3
3
88
80
Cl
MeO
3m
3n
O
MeO
OMe
O
Cl
O
O
OMe
O
O
4
5
2b
2b
0.02
0.02
1
1
85
91
Cl
Cl
1d
1h
3o
3p
OMe
OMe
O
O
6
7
Cl
0.02
0.02
3
3
92
95
Cl
O
2c
1a
1c
O
3q
3r
Cl
2c
2c
Cl
O
Cl
O
8
0.02
1
85
Cl
1h
3s
O
O
Cl
OMe
O
MeO
9
0.02
0.02
0.02
6
3
6
90
83
85
Cl
2d
1a
3t
O
O
OMe
10
11
2d
Cl
Cl
1h
1a
O
3u
3v
2e
2f
O
O
12
13
1a
0.02
0.02
3
3
88
74
3w
3x
1a
1a
NO
2
2g
2h
O
NO
2
14
0.02
3
93
O
3y
3z
O
15
16
2h
2h
0.02
0.02
3
3
91
84
Cl
1c
O
O
Cl
O
1d
3aa
O
Cl
17
2h
0.02
3
87
Cl
Cl
1e
3ab

10138
Table 3 (continued)
J.-Y. Chen et al. / Tetrahedron 65 (2009) 10134–10141
Entry
Acyl chloride
Alkyne
2h
[Pd] (mol %)
0.02
Time (h)
Product
Yieldb (%)
O
O
18
3
1
85
88
Cl
1h
1i
O
3ac
3ad
O
19
2h
0.02
Cl
O
20
1i
0.02
9
25
2i
3ae
a
Reaction conditions: in Et3N at 50 ꢀC. [acyl chloride]:[terminal alkyne]¼1.3:1. [NS-MCM-41–Pd]:[PPh3]:[CuI]¼1:2:2.
b
Isolated yields.
melting point apparatus and were uncorrected. All 1H and 13C NMR
0.006 mmol), Et3N (20 mL), terminal alkyne (15 mmol), and acyl
chloride (19.5 mmol), then the reaction mixture was stirred at 50 ꢀC
for the indicated reaction time period (see Tables 2–4). After
cooling to room temperature, the resulting solution was passed
through a short silica gel column using EtOAc as the eluent to
remove the ammonium salt. The solvent was then removed in
a vacuum and the desired product was purified by silica gel column
chromatography.
spectra were recorded in CDCl3 or C6D6 solutions at 25 ꢀC on Varian
200 NMR spectrometers. GC analysis was performed on an SRI
8610C equipped with a fused silica capillary column.
4.2. General procedure for the coupling of acid chlorides and
terminal alkynes
Under a nitrogen atmosphere, a Schlenk tube was charged with
NS-MCM-41–Pd (20 mg, 0.003 mmol, in the case of 0.02 mol %
catalyst loading), PPh3 (1.6 mg, 0.006 mmol), CuI (1.1 mg,
4.2.1. 1,3-Diphenylpropynone (3a). Yellow liquid.3e 1H NMR (CDCl3,
200 MHz)
d
8.24 (d, J¼8.3 Hz, 2H), 7.70 (d, J¼7.7 Hz, 2H), 7.43–7.65
Table 4
NS-MCM-41–Pd-catalyzed coupling of acyl chlorides with aliphatic terminal alkynesa
Entry
1
Acyl chloride
Alkyne
[Pd] (mol %)
Time (h)
6
Product
Yieldb (%)
86
O
O
(CH2)3CH3
0.1
0.1
0.1
Cl
2j
(CH ) CH
2 3
4a
4b
4c
1a
1b
1c
3
O
O
2
3
Cl
2j
2j
12
12
75
79
(CH2)3CH3
MeO
MeO
O
O
Cl
(CH2)3CH3
O
O
O
Cl
O
Cl
4
5
2j
2j
0.1
0.1
6
3
88
82
(CH ) CH
1d
1h
4d
4e
2 3
3
(CH ) CH
2 3
3
O
O
6
7
8
2j
0.1
0.1
0.1
3
6
6
78
98
63
Cl
(CH ) CH
3
4f
1i
1a
1h
2 3
O
O
O
(CH2)5CH3
Cl
2k
(CH ) CH
2 5
3
4g
O
2k
Cl
(CH2)5CH3
4h
4i
O
O
9
0.1
6
84
Cl
2l
1a
a
Reaction conditions: in Et3N at 50 ꢀC. [acyl chloride]:[terminal alkyne]¼1.3:1. [NS-MCM-41–Pd]:[PPh3]:[CuI]¼1:2:2.
b
Isolated yields.

J.-Y. Chen et al. / Tetrahedron 65 (2009) 10134–10141
10139
NS-MCM-41-Pd (0.1 mol%)
PPh3 (0.2 mol%)
O
O
CuI (0.2 mol%)
Cl
+
Et3N, 50 °C, 0.5 h
First run: 98%
First recycled run: 98%
Second recycled run: 97%
Third recycled run: 93%
Fourth recycled run: 90%
Scheme 2. Recycling studies of the NS-MCM-41–Pd-catalyzed coupling of cyclohexanecarbonyl chloride with phenylacetylene.
(m, 6H); 13C NMR (CDCl3, 50 MHz)
130.3, 129.1 (2C), 128.2 (2C), 128.1, 119.7, 92.9, 86.7.
d
177.2, 136.3, 133.6 (2C), 132.6,
1.28 (s, 9H); 13C NMR (CDCl3, 50 MHz)
128.5 (2C), 120.2, 92.1, 85.9, 44.8, 26.1 (3C).
d 193.9, 132.8 (2C), 130.4,
4.2.2. 1-(4-Methoxyphenyl)-3-phenylpropynone (3b). Pale yellow
4.2.11. 1-Phenylhept-1-yn-3-one (3k). Yellow liquid.19 1H NMR
(CDCl3, 200 MHz) 7.56–7.61 (m, 2H), 7.33–7.46 (m, 3H), 2.67 (t,
J¼7.4 Hz, 2H),1.66–1.81 (m, 2H),1.26–1.49 (m, 2H), 0.95 (t, J¼7.2 Hz,
3H); 13C NMR (CDCl3, 50 MHz)
187.9, 132.8 (2C), 130.5, 128.5 (2C),
solid. Mp 99–100 ꢀC (lit.16 100–101 ꢀC). 1H NMR (CDCl3, 200 MHz)
d
d
8.18 (d, J¼8.8 Hz, 2H), 7.66 (d, J¼8.0 Hz, 2H), 7.39–7.47 (m, 3H),
6.97 (d, J¼8.8 Hz, 2H), 3.88 (s, 3H); 13C NMR (CDCl3, 50 MHz)
d
d
175.2, 163.2, 131.6 (2C), 130.6 (2C), 129.3, 128.9, 127.3 (2C), 119.1,
120.1, 90.4, 87.8, 45.2, 29.2, 22.1, 13.7.
112.6 (2C), 90.9, 85.7, 54.3.
4.2.12. 3-(4-Methoxyphenyl)-1-phenylpropynone (3l). Pale yellow
4.2.3. 3-Phenyl-1-p-tolylpropynone (3c). Pale yellow solid. Mp
solid. Mp 81–83 ꢀC (lit.16 81–82 ꢀC). 1H NMR (CDCl3, 200 MHz)
87–88 ꢀC (lit.17 86–88 ꢀC). 1H NMR (CDCl3, 200 MHz)
d
8.07 (d,
J¼8.2 Hz, 2H), 7.63 (d, J¼7.2 Hz, 2H), 7.21–7.40 (m, 5H), 2.40 (s, 3H);
13C NMR (CDCl3, 50 MHz)
177.4, 145.1, 134.5, 132.8 (2C), 130.5,
d
8.20 (d, J¼8.4 Hz, 2H), 7.46–7.65 (m, 5H), 6.90 (d, J¼8.4 Hz, 2H),
3.83 (s, 3H); 13C NMR (CDCl3, 50 MHz)
d
177.8, 161.6, 136.9, 134.9
d
(2C), 133.7, 129.3 (2C), 128.4 (2C), 114.3 (2C), 111.7, 94.2, 86.8, 55.3.
129.5 (2C), 129.2 (2C), 128.5 (2C), 120.1, 92.4, 86.9, 21.7.
4.2.13. 1,3-Bis-(4-methoxyphenyl)propynone (3m). Pale yellow
4.2.4. 3-Phenyl-1-o-tolylpropynone (3d). Yellow liquid.18 1H NMR
solid. Mp 73–75 ꢀC (lit.20 72–77 ꢀC). 1H NMR (CDCl3, 200 MHz)
(CDCl3, 200 MHz)
d
8.30 (d, J¼7.6 Hz, 1H), 7.64–7.69 (m, 3H), 7.26–7.52
d
8.20 (d, J¼8.8 Hz, 2H), 7.99 (d, J¼8.8 Hz, 2H), 7.64 (d, J¼8.3 Hz, 2H),
(m, 5H), 2.68 (s, 3H); 13C NMR (CDCl3, 50 MHz)
d
178.2, 139.1, 134.4,
6.96 (d, J¼8.3 Hz, 2H), 3.90 (s, 3H), 3.86 (s, 3H); 13C NMR (CDCl3,
131.9,131.6(2C),130.9,129.3(2C),127.3(2C),124.6,119.1, 90.5,87.2,20.7.
50 MHz) d 176.5, 164.2, 161.4, 134.8 (2C), 131.6 (2C), 128.5, 119.6,
114.3 (2C), 113.7 (2C), 93.2, 86.7, 55.3, 55.2.
4.2.5. 1-(4-Chlorophenyl)-3-phenylpropynone (3e). Pale yellow
solid. Mp 105–106 ꢀC (lit.16 107–108 ꢀC). 1H NMR (CDCl3, 200 MHz)
4.2.14. 3-(4-Methoxyphenyl)-1-p-tolylpropynone (3n). Pale yellow
d
8.16 (d, J¼8.8 Hz, 2H), 7.70 (d, J¼7.9 Hz, 2H), 7.52–7.40 (m, 5H); 13
C
solid. Mp 93–94 ꢀC (lit.20 93.5–94.5 ꢀC). 1H NMR (CDCl3, 200 MHz)
NMR (CDCl3, 50 MHz)
d
176.4, 140.6, 135.3, 132.9 (2C), 130.8, 130.7
d
8.09 (d, J¼8.4 Hz, 2H), 7.62 (d, J¼8.4 Hz, 2H), 7.28 (d, J¼8.2 Hz, 2H),
(2C), 128.8 (2C), 128.6 (2C), 119.8, 93.5, 86.5.
6.91 (d, J¼8.4 Hz, 2H), 3.84 (s, 3H), 2.43 (s, 3H); 13C NMR (CDCl3,
50 MHz)
d 177.6, 161.5, 144.8, 134.9 (2C), 129.5 (2C), 129.2 (2C),
4.2.6. 1-Furan-2-yl-3-phenylpropynone (3f). Brown solid. Mp 50–
128.6, 114.3 (2C), 111.9, 93.6, 86.8, 55.3, 21.7.
51 ꢀC (lit.2a 49–51 ꢀC). 1H NMR (CDCl3, 200 MHz)
d 7.64–7.71 (m,
3H), 7.38–7.50 (m, 4H), 6.62 (dd, J¼3.8, 1.8 Hz, 1H); 13C NMR (CDCl3,
4.2.15. 3-(4-Methoxyphenyl)-1-o-tolylpropynone (3o). Yellow liq-
50 MHz)
d
164.7, 153.2, 147.9, 132.9 (2C), 130.8, 128.6 (2C), 120.8,
uid. 1H NMR (CDCl3, 200 MHz)
d
8.39 (d, J¼8.4 Hz, 1H), 7.85–7.38
119.9, 112.6, 91.8, 86.2.
(m, 5H), 7.04 (d, J¼8.4 Hz, 2H), 3.98 (s, 3H), 2.79 (s, 3H); 13C NMR
(CDCl3, 50 MHz)
d 179.7, 161.4, 140.0, 135.9, 134.7 (2C), 132.7, 132.5,
4.2.7. 3-Phenyl-1-thiophen-2-yl-propynone (3g). Brown solid. Mp
131.9, 128.7, 125.7, 114.3 (2C), 92.8, 88.3, 55.3, 21.7. HRMS Calcd for
C17H14O2: 250.0994; found: 250.0986.
55–56 ꢀC (lit.3g 53–54 ꢀC). 1H NMR (CDCl3, 200 MHz)
d
8.00–8.03
(m, 1H), 7.65–7.75 (m, 3H), 7.38–7.49 (m, 3H), 7.17–7.21 (m, 1H); 13C
NMR (CDCl3, 50 MHz) 169.6, 144.8, 135.1, 134.9, 132.9 (2C), 130.7,
d
4.2.16. 1-Cyclohexyl-3-(4-methoxyphenyl)propynone (3p). Yellow
128.6 (2C), 128.2, 119.8, 91.6, 86.4.
liquid.21 1H NMR (CDCl3, 200 MHz)
d
7.51 (d, J¼8.6 Hz, 2H), 6.78 (d,
J¼8.6 Hz, 2H), 3.82 (s, 3H), 2.41–2.52 (m, 1H), 2.01–2.06 (m, 2H),
1.29–1.77 (m, 8H); 13C NMR (CDCl3, 50 MHz)
189.9, 160.2, 133.6
4.2.8. 1-Cyclohexyl-3-phenylpropynone (3h). Yellow liquid.2a 1H
d
NMR (CDCl3, 200 MHz)
2.44–2.57 (m, 1H), 2.03–2.09 (m, 2H), 1.20–1.87 (m, 8H); 13C NMR
(CDCl3, 50 MHz) 189.9, 131.6 (2C), 129.2, 127.2 (2C), 118.9, 89.9,
d
7.60 (d, J¼7.6 Hz, 2H), 7.36–7.49 (m, 3H),
(2C), 113.0 (2C), 110.6, 91.1, 85.8, 54.0, 50.9, 27.1 (2C), 24.6, 24.1
(2C).
d
85.9, 50.9, 27.1 (2C), 24.5, 24.1 (2C).
4.2.17. 3-(4-Chlorophenyl)-1-phenylpropynone (3q). Pale yellow
solid. Mp 107–108 ꢀC (lit.16 105–106 ꢀC). 1H NMR (CDCl3, 200 MHz)
4.2.9. 4-Methyl-1-phenylpent-1-yn-3-one (3i). Yellow liquid.2a 1H
d
8.21 (d, J¼8.4 Hz, 2H), 7.49–7.69 (m, 5H), 7.41 (d, J¼8.4 Hz, 2H); 13
C
NMR (CDCl3, 200 MHz)
d
7.60 (d, J¼7.9 Hz, 2H), 7.34–7.46 (m, 3H),
NMR (CDCl3, 50 MHz) d 177.5, 137.1, 136.6, 134.1 (3C), 129.4 (2C),
2.77 (hep, J¼6.8 Hz, 1H), 1.27 (d, J¼6.8 Hz, 6H); 13C NMR (CDCl3,
129.0 (2C), 128.5 (2C), 118.5, 91.5, 87.5.
50 MHz)
17.1 (2C).
d 191.3, 132.4 (2C), 130.2, 128.4 (2C), 119.7, 91.1, 86.5, 42.7,
4.2.18. 3-(4-Chlorophenyl)-1-p-tolylpropynone (3r). Pale yellow
solid. Mp 135–137 ꢀC. 1H NMR (CDCl3, 200 MHz)
8.08 (d, J¼8.2 Hz,
2H), 7.60 (d, J¼8.6 Hz, 2H), 7.39 (d, J¼8.6 Hz, 2H), 7.30 (d, J¼8.2 Hz,
2H), 2.43 (s, 3H); 13C NMR (CDCl3, 50 MHz)
177.2, 154.2, 136.9, 134.4,
d
4.2.10. 4,4-Dimethyl-1-phenylpent-1-yn-3-one (3j). Yellow liquid.2a
1H NMR (CDCl3, 200 MHz)
7.56–7.61 (m, 2H), 7.38–7.46 (m, 3H),
d
d

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J.-Y. Chen et al. / Tetrahedron 65 (2009) 10134–10141
134.1 (2C), 129.5 (2C), 129.3 (2C), 128.9 (2C), 118.6, 90.0, 87.6, 21.7;
Anal. Calcd for C16H11ClO: C, 75.45, H, 4.35; Found: C, 75.44, H, 4.84.
200 MHz)
d
8.39 (d, J¼8.2 Hz, 1H), 8.24 (d, J¼8.6 Hz, 2H), 7.91–8.11
176.4, 140.6,
(m, 3H), 7.57–7.75 (m, 5H); 13C NMR (CDCl3, 50 MHz)
d
135.4, 133.5, 133.2, 133.1, 131.6, 130.7 (2C), 128.9 (2C), 128.5, 127.7,
126.9, 125.6, 125.1, 117.4, 91.9, 91.3.
4.2.19. 3-(4-Chlorophenyl)-1-cyclohexylpropynone (3s). Pale yellow
solid. Mp 50–52 ꢀC. 1H NMR (CDCl3, 200 MHz)
d
7.51 (d, J¼8.6 Hz,
2H), 7.37 (d, J¼8.6 Hz, 2H), 2.43–2.57 (m, 1H), 2.02–2.08 (m, 2H),
1.19–1.84 (m, 8H); 13C NMR (CDCl3, 50 MHz)
190.9, 136.7, 134.0
4.2.29. 1-Cyclohexyl-3-naphthalen-1-ylpropynone (3ac). Pale yel-
d
low solid. Mp 55–56 ꢀC. 1H NMR (CDCl3, 200 MHz)
d 8.30 (d,
(2C), 128.9 (2C), 118.6, 89.6, 78.8, 52.2, 28.2 (2C), 25.7, 25.3 (2C);
Anal. Calcd for C15H15ClO: C, 73.02, H, 6.13; Found: C, 72.58, H, 6.21.
J¼8.2 Hz, 1H), 7.80–7.96 (m, 3H), 7.23–7.67 (m, 3H), 2.48–2.61 (m,
1H), 2.10–2.15 (m, 2H), 1.23–1.87 (m, 8H); 13C NMR (CDCl3, 50 MHz)
d
191.1, 136.5, 133.5, 132.9, 131.1, 128.4, 127.5, 126.7, 125.6, 125.1,
4.2.20. 3-(2-Methoxyphenyl)-1-phenylpropynone (3t). Pale yellow
117.7, 91.9, 89.5, 52.4, 28.4 (2C), 25.8, 25.4 (2C). HRMS Calcd for
C19H18O: 262.1358; found: 262.1350.
solid. Mp 74–75 ꢀC (lit.22 72–73.5 ꢀC). 1H NMR (CDCl3, 200 MHz)
d
8.32 (d, J¼7.0 Hz, 2H), 7.42–7.67 (m, 5H), 6.94–7.04 (m, 2H), 3.98
(s, 3H); 13C NMR (CDCl3, 50 MHz)
d
177.9, 161.7, 137.1, 134.8, 133.7,
4.2.30. 4-Methyl-1-naphthalen-1-ylpent-1-yn-3-one (3ad). Yellow
132.5, 129.6 (2C), 128.4 (2C), 120.6, 110.8, 109.4, 91.2, 90.5, 55.8.
liquid. 1H NMR (CDCl3, 200 MHz)
d
8.33 (d, J¼8.0 Hz, 1H), 7.84–7.98
(m, 3H), 7.44–7.65 (m, 3H), 2.88 (hep, J¼6.8 Hz, 1H), 1.35 (d,
4.2.21. 1-Cyclohexyl-3-(2-methoxyphenyl)propynone (3u). Yellow
J¼6.8 Hz, 6H); 13C NMR (CDCl3, 50 MHz)
d 190.6, 132.3, 131.8, 130.1,
liquid. 1H NMR (CDCl3, 200 MHz)
d
7.51 (d, J¼8.5 Hz, 2H), 7.36 (d,
129.6, 127.2, 126.3, 125.6, 124.4, 123.8, 116.4, 90.3, 88.5, 41.9, 16.9
(2C). HRMS Calcd for C16H14O: 222.1045; found: 222.1040.
J¼8.5 Hz, 2H), 7.26–7.29 (m, 2H), 3.92 (s, 3H), 2.45–2.56 (m, 1H),
2.02–2.18 (m, 2H), 1.26–1.80 (m, 8H); 13C NMR (CDCl3, 50 MHz)
d
191.3, 161.4, 134.7, 132.2, 120.4, 110.7, 109.3, 91.3, 88.7, 55.7, 55.3,
4.2.31. 3-Anthracen-9-yl-1-phenylpropynone (3ae). Yellow solid.
28.3 (2C), 25.8, 25.3 (2C). HRMS Calcd for C16H18O2: 242.1307;
found: 242.1319.
Mp 113–116 ꢀC. 1H NMR (CDCl3, 200 MHz)
d
8.64 (d, J¼9.0 Hz, 2H),
8.60 (s, 1H), 8.28–8.41 (m, 5H), 8.06 (d, J¼8.4 Hz, 2H), 7.52–7.78 (m,
4H); 13C NMR (CDCl3, 50 MHz)
177.8, 137.3, 133.9 (2C), 131.1, 130.9
d
4.2.22. 1-Phenyl-3-o-tolylpropynone (3v). Yellow liquid.23 1H NMR
(2C), 129.6 (2C), 128.9 (2C), 128.7 (2C), 127.9 (2C), 127.1, 126.1 (2C),
115.9 (2C), 113.4, 98.2, 90.3. HRMS Calcd for C23H14O: 306.1045;
found: 306.1054.
(CDCl3, 200 MHz)
d
8.24 (d, J¼8.2 Hz, 2H), 7.48–7.68 (m, 5H), 7.28–
7.37 (m, 2H), 2.40 (s, 3H); 13C NMR (CDCl3, 50 MHz)
d
177.6, 141.9,
136.8, 133.8, 133.4, 130.6, 129.7, 129.2 (2C), 128.4 (2C), 125.7, 119.8,
91.9, 90.6, 20.6.
4.2.32. 1-Phenylhept-2-yn-1-one (4a). Pale yellow liquid.2a 1H NMR
(CDCl3, 200 MHz)
d 8.09–8.11 (m, 2H), 7.42–7.58 (m, 3H), 2.47 (d,
4.2.23. 1-Phenyl-3-p-tolylpropynone (3w). Pale yellow solid. Mp
J¼7.2 Hz, 2H), 1.45–1.82 (m, 4H), 0.93 (t, J¼7.2 Hz, 3H); 13C NMR
68–69 ꢀC (lit.16 67–68 ꢀC). 1H NMR (CDCl3, 200 MHz)
d
8.21
(d, J¼8.0 Hz, 2H), 7.51–7.62 (m, 5H), 7.22 (d, J¼8.0 Hz, 2H), 2.39 (s,
3H); 13C NMR (CDCl3, 50 MHz)
177.8,141.4,136.9, 133.9,132.9 (2C),
(CDCl3, 50 MHz) d 177.4, 136.3, 133.3, 129.1 (2C), 127.9 (2C), 96.6,
79.5, 30.1, 22.4, 19.2, 13.9.
d
129.5 (2C), 129.3 (2C), 128.5 (2C), 116.9, 93.7, 86.7, 21.7.
4.2.33. 1-(4-Methoxyphenyl)hept-2-yn-1-one (4b). Pale yellow liq-
uid.25 1H NMR (CDCl3, 200 MHz)
d
8.11 (d, J¼8.6 Hz, 2H), 6.95 (d,
4.2.24. 3-(4-Nitrophenyl)-1-phenylpropynone (3x). Orange solid.
J¼8.6 Hz, 2H), 3.88 (s, 3H), 2.50 (t, J¼6.8 Hz, 2H), 1.41–1.74 (m, 4H),
Mp 146–148 ꢀC (lit.16 148–150 ꢀC). 1H NMR (CDCl3, 200 MHz)
d
8.31
(d, J¼9.0 Hz, 2H), 8.21 (d, J¼7.0 Hz, 2H), 7.85 (d, J¼9.0 Hz, 2H),
7.51–7.72 (m, 3H); 13C NMR (CDCl3, 50 MHz)
177.3, 148.5, 136.3,
0.97 (t, J¼7.0 Hz, 3H); 13C NMR (CDCl3, 50 MHz)
d 176.7, 164.1, 131.7
(2C), 130.2, 113.6 (2C), 95.7, 79.5, 55.4, 29.8, 21.9, 18.7, 13.4.
d
134.6, 133.6 (2C), 129.5 (2C), 128.7 (2C), 126.7, 123.7 (2C), 89.8, 89.1.
4.2.34. 1-p-Tolylhept-2-yn-1-one (4c). Pale yellow liquid.25 1H NMR
(CDCl3, 200 MHz)
d
8.01 (d, J¼8.0 Hz, 2H), 7.25 (d, J¼7.8 Hz, 2H),
4.2.25. 3-Naphthalen-1-yl-1-phenylpropynone (3y). Pale yellow
2.47 (t, J¼6.8 Hz, 2H), 2.40 (s, 3H), 1.42–1.68 (m, 4H), 0.94 (t,
solid.3e Mp 81–83 ꢀC. 1H NMR (CDCl3, 200 MHz)
d
8.41 (d, J¼8.4 Hz,
1H), 8.31 (d, J¼8.0 Hz, 2H), 7.93–7.97 (m, 2H), 7.87 (d, J¼8.4 Hz, 1H),
7.48–7.67 (m, 6H); 13C NMR (CDCl3, 50 MHz)
177.2, 136.5, 133.7,
J¼7.1 Hz, 3H); 13C NMR (CDCl3, 50 MHz)
d 177.6, 144.6, 134.5, 129.4
(2C), 128.9 (2C), 95.9, 79.6, 29.7, 21.9, 21.5, 18.7, 13.3.
d
133.2, 132.7, 132.6, 131.1, 129.2 (2C), 128.3 (2C), 128.2, 127.3, 126.5,
125.4, 124.8, 117.3, 91.5, 91.3.
4.2.35. 1-o-Tolylhept-2-yn-1-one (4d). Pale yellow liquid.25 1H NMR
(CDCl3, 200 MHz)
3H), 2.45 (t, J¼7.1 Hz, 2H), 1.41–1.66 (m, 4H), 0.93 (t, J¼7.1 Hz, 3H);
13C NMR (CDCl3, 50 MHz)
179.8, 140.1, 135.7, 132.9, 132.4, 131.9,
d
8.17 (d, J¼7.6 Hz, 1H), 7.19–7.41 (m, 3H), 2.60 (s,
4.2.26. 3-Naphthalen-1-yl-1-p-tolylpropynone (3z). Pale yellow
d
solid. Mp 80–81 ꢀC (lit.24 78–80 ꢀC). 1H NMR (CDCl3, 200 MHz)
125.6, 95.2, 81.1, 29.8, 21.9, 21.7, 18.7, 13.4.
d
8.42 (d, J¼8.0 Hz, 1H), 8.20 (d, J¼8.2 Hz, 2H), 7.88–7.99 (m, 3H),
7.48–7.69 (m, 3H), 7.35 (d, J¼8.2 Hz, 2H), 2.40 (s, 3H); 13C NMR
4.2.36. 1-Cyclohexylhept-2-yn-1-one (4e). Pale yellow liquid.2a 1H
(CDCl3, 50 MHz)
d
178.6, 145.1, 134.7, 133.5, 133.1, 132.9, 131.2, 129.6
NMR (CDCl3, 200 MHz)
d
2.38 (d, J¼6.8 Hz, 2H), 1.22–1.99 (m, 15H),
(2C), 129.3 (2C), 128.5, 127.6, 126.8, 125.7, 125.1, 117.8, 91.7, 90.8,
21.8.
0.93 (t, J¼7.0 Hz, 3H); 13C NMR (CDCl3, 50 MHz)
d 191.3, 94.6, 80.0,
52.1, 29.7, 28.2 (2C), 25.7, 25.3 (2C), 21.8, 18.5, 13.3.
4.2.27. 3-Naphthalen-1-yl-1-o-tolylpropynone (3aa). Pale yellow
4.2.37. 2-Methylnon-4-yn-3-one (4f). Pale yellow liquid.2a 1H NMR
solid. Mp 72–73 ꢀC. 1H NMR (CDCl3, 200 MHz)
d
8.37–8.44 (m, 2H),
7.86–7.97 (m, 3H), 7.28–7.67 (m, 6H), 2.72 (s, 3H); 13C NMR (CDCl3,
50 MHz) 179.5, 140.3, 135.8, 133.6, 132.9, 132.7, 132.1, 131.8, 131.1,
(CDCl3, 200 MHz)
d
2.62 (hep, J¼7.0 Hz, 1H), 2.38 (t, J¼6.9 Hz, 2H),
1.16–1.62 (m, 4H), 1.18 (d, J¼7.0 Hz, 6H), 0.93 (t, J¼7.0 Hz, 3H); 13C
d
NMR (CDCl3, 50 MHz)
(2C), 13.3.
d 192.0, 94.9, 79.7, 42.9, 29.7, 21.8, 18.5, 17.9
128.4, 127.5, 126.7, 125.8, 125.7, 124.9, 124.8, 117.8, 93.1, 90.1, 21.8.
HRMS Calcd for C20H14O: 270.1045; found: 270.1040.
4.2.38. 1-Phenylnon-2-yn-1-one (4g). Pale yellow liquid.25 1H NMR
(CDCl3, 200 MHz) 8.12–8.17 (m, 2H), 7.43–7.64 (m, 3H), 2.51 (t,
J¼6.8 Hz, 2H),1.61–1.75 (m, 2H),1.29–1.75 (m, 6H), 0.91 (t, J¼6.6 Hz,
4.2.28. 1-(4-Chlorophenyl)-3-naphthalen-1-ylpropynone (3ab). Pale
d
yellow solid. Mp 116–117 ꢀC (lit.17 115–116 ꢀC). 1H NMR (CDCl3,

J.-Y. Chen et al. / Tetrahedron 65 (2009) 10134–10141
10141
3H); 13C NMR (CDCl3, 50 MHz)
d 177.5,136.5, 133.4, 129.0 (2C),128.0
(2C), 96.3, 79.3, 30.9, 28.2, 27.4, 22.1, 18.8, 13.6.
Org. Lett. 2004, 6, 3151; (f) Cox, R. J.; Ritson, D. J.; Dane, T. A.; Berge, J.;
Charmant, J. P. H.; Kantacha, A. Chem. Commun. 2005, 1037; (g) Palimkar, S. S.;
Kumar, P. H.; Jogdand, N. R.; Daniel, T.; Lahoti, R. J.; Srinivasan, K. V. Tetrahedron
Lett. 2006, 47, 5527; (h) Palimkar, S. S.; Lahoti, R. J.; Srinivasan, K. V. Green Chem.
2007, 9, 146; (i) Liu, H.-L.; Jiang, H.-F.; Zhang, M.; Yao, W.-J.; Zhu, Q.-H.; Tang, Z.
Tetrahedron Lett. 2008, 49, 3805; (j) Lv, Q.-R.; Meng, X.; Wu, J.-S.; Gao, Y.-J.; Li,
C.-L.; Zhu, Q.-Q.; Chen, B.-H. Catal. Commun. 2008, 9, 2127; (k) Nishihara, Y.;
Inoue, E.; Okada, Y.; Takagi, K. Synlett 2008, 3045.
4.2.39. 1-Cyclohexylnon-2-yn-1-one (4h). Pale yellow liquid.26 1H
NMR (CDCl3, 200 MHz)
d 2.33–2.40 (m, 3H), 1.22–1.99 (m, 18H),
0.90 (t, J¼7.0 Hz, 3H); 13C NMR (CDCl3, 50 MHz)
d 191.5, 94.8, 80.1,
4. Likhar, P. R.; Subhas, M. S.; Roy, M.; Roy, S.; Kantam, M. L. Helv. Chim. Acta 2008,
91, 259.
52.2, 31.1, 28.4, 28.2 (2C), 27.7, 25.7, 25.3 (2C), 22.4, 18.9, 13.9.
5. For recent reviews, see: (a) Anwander, R. Chem. Mater. 2001, 13, 4419; (b) Biffis,
A.; Zecca, M.; Basato, M. J. Mol. Catal. A: Chem. 2001, 173, 249; (c) He, X.; An-
tonelli, D. Angew. Chem., Int. Ed. 2002, 41, 214; (d) De Vos, D. E.; Dams, M.; Sels,
B. F.; Jacobs, P. A. Chem. Rev. 2002, 102, 3615; (e) Trong On, D.; Desplantier-
Giscard, D.; Danumah, C.; Kaliaguine, S. Appl. Catal. A: Gen. 2003, 253, 545; (f)
Thomas, J. M.; Raja, R. J. Organomet. Chem. 2004, 689, 4110; (g) Li, C. Catal. Rev.
2004, 46, 419; (h) Taguchi, A.; Schu¨th, F. Microporous Mesoporous Mater. 2005,
77, 1; (i) Hoffmann, F.; Cornelius, M.; Morell, J.; Fro¨ba, M. Angew. Chem., Int. Ed.
2006, 45, 3216; (j) Ko¨hler, K.; Pro¨ckl, S. S.; Kleist, W. Curr. Org. Chem. 2006, 10,
1585.
6. (a) Mehnert, C. P.; Weaver, D. W.; Ying, J. Y. J. Am. Chem. Soc. 1998, 120, 12289;
(b) Clark, J. H.; Macquarrie, D. J.; Mubofu, E. B. Green Chem. 2000, 2, 53; (c)
Zhou, J.; Zhou, R.; Mo, L.; Zhao, S.; Zheng, X. J. Mol. Catal. A: Chem. 2002, 178,
289; (d) Yang, H.; Zhang, G.; Hong, X.; Zhu, Y. J. Mol. Catal. A: Chem. 2004, 210,
143; (e) Venkatesan, C.; Singh, A. P. J. Catal. 2004, 227, 148; (f) Gonza´lez-Are-
4.2.40. 3-Cyclohex-1-enyl-1-phenylpropynone (4i). Pale yellow liq-
uid.3e 1H NMR (CDCl3, 200 MHz)
d
8.14 (d, J¼8.2 Hz, 2H), 7.44–7.60
(m, 3H), 6.59 (m, 1H), 2.20–2.30 (m, 4H), 1.63–1.74 (m, 4H); 13C
NMR (CDCl3, 50 MHz) 177.8, 142.5, 136.8, 133.6, 129.2 (2C), 128.3
d
(2C), 118.9, 95.5, 85.0, 28.2, 26.0, 21.8, 20.9.
4.3. Experimental procedure for the recycling of
NS-MCM-41–Pd
This procedure was conducted as described above: cyclo-
hexanecarbonyl chloride (19.5 mmol), phenylacetylene (15 mmol),
PPh3 (7.9 mg, 0.03 mmol), CuI (5.7 mg, 0.03 mmol), NS-MCM-41-Pd
(100 mg, 0.015 mmol), and Et3N (20 mL) were used in this case, and
the reaction time for each cycle was fixed at 0.5 h at 50 ꢀC. After
the reaction, the catalyst was collected by centrifugation, washed
alternately with 3 N HCl aqueous solution and THF twice (20 mL for
each wash), and dried in vacuum overnight. The recovered catalyst
was then re-used in the same reaction under identical conditions.
The product in each cycle was isolated from the collected solution
by the usual workup procedures.
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Acknowledgements
This research was financially supported by the National Science
Council of Taiwan (NSC95-2113-M-027-001).
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