Microwave-assisted coupling reaction by copper(I)-catalyzed of terminal alkynes with aroyl chlorides

Article abstract of DOI:10.1081/SCC-100106214

A rapid and efficient method for synthesis of α,β-conjugated acetylenic ketones involves reaction of phenylacetylene with aroyl chlorides in the presence of catalytic amount CuI under microwave irradiation to give the corresponding α,β-conjugated acetylen

Full text of DOI:10.1081/SCC-100106214

This article was downloaded by: [University of Connecticut]
On: 12 October 2014, At: 12:47
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer
House, 37-41 Mortimer Street, London W1T 3JH, UK
Synthetic Communications: An International Journal
for Rapid Communication of Synthetic Organic
Chemistry
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lsyc20
MICROWAVE-ASSISTED COUPLING REACTION BY
COPPER(I)-CATALYZED OF TERMINAL ALKYNES WITH
AROYL CHLORIDES
a
a
a
a
a
Jin-Xian Wang , Bangguo Wei , Yulai Hu , Zhanxiang Liu & Ying Fu
a
Department of Chemistry , Institute of Chemistry Northwest Normal University , 805 An
Ning Road (E.), Lanzhou, 730 070, P. R. China
Published online: 22 Aug 2006.
To cite this article: Jin-Xian Wang , Bangguo Wei , Yulai Hu , Zhanxiang Liu & Ying Fu (2001) MICROWAVE-ASSISTED
COUPLING REACTION BY COPPER(I)-CATALYZED OF TERMINAL ALKYNES WITH AROYL CHLORIDES, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry, 31:22, 3527-3532, DOI: 10.1081/
SCC-100106214
To link to this article: http://dx.doi.org/10.1081/SCC-100106214
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of
the Content. Any opinions and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied
upon and should be independently verified with primary sources of information. Taylor and Francis shall
not be liable for any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other
liabilities whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or
arising out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions

SYNTHETIC COMMUNICATIONS, 31(22), 3527–3532 (2001)
MICROWAVE-ASSISTED
COUPLING REACTION BY
COPPER(I)-CATALYZED OF
TERMINAL ALKYNES WITH
AROYL CHLORIDES
Jin-Xian Wang,* Bangguo Wei, Yulai Hu,
ZhanxiangLiu, and YingFu
Institute of Chemistry, Department of Chemistry,
Northwest Normal University, 805 An Ning
Road (E.), Lanzhou, 730 070, P. R. China
ABSTRACT
A rapid and efficient method for synthesis of a,b-conjugated
acetylenic ketones involves reaction of phenylacetylene with
aroyl chlorides in the presence of catalytic amount CuI under
microwave irradiation to give the corresponding a,b-conju-
gated acetylenic ketones 3 a–i in 76–93% yields.
a,b-Conjugated acetylenic ketones compounds are highly valuable
precursors or intermediates in synthetic organic chemistry, and many of
1
2
them are of biological interest. One of the most efficient methods for the
synthesis of a,b-conjugated acetylenic ketones involves the reaction of a
metal acetylide with an acyl chlorides or another carboxylic acid derivative.
3
*
Corresponding author.
3
527
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

ORDER
REPRINTS
3
528
WANG ET AL.
Recently, the direct coupling reaction between an acyl chloride and terminal
4
alkynes catalyzed by CuI or Pd(PPh ) Cl -CuI have been described.
5
3
2
2
However, many of these reactions suffer from lack of generality, poor
ꢁ
3h
yield, long reaction time and even require low temperature (ꢀ78 C).
This communication describes a very convenient method for the synthesis
of a,b-conjugated acetylenic ketones by the reaction of 1-alkynes with aroyl
chlorides in the presence of catalystic amount CuI under microwave irradia-
tion conditions.
In recent years, interest has been shown in the study of microwave
assisted organic reactions in polar solvents or in absent of solvent and some
6
important reviews have been published. Microwave irradiation has also
been applied to several organic reactions. Recently, we have also reported
7
8
the synthesis of dibenzyl diselenide, diaroyl diselenides under microwave
irradiation conditions. We now wish to report the synthesis of a,b-conju-
gated acetylenic ketones from phenylacetylene with aroyl chloride using CuI
as catalyst under microwave irradiation. This method is simple, fast and
affords good yields. The reactions are shown in Scheme 1 and results are
summarized in Table 1.
Scheme 1.
Using the reaction of phenylacetylene with benzoyl chloride as an
example, we investigated the effects of various catalysts on the formation
of 3a, and results are summarized in Table 2. The results show that CuI is
the best catalyst for the reactions, because Pd(II) reagent is very expensive
and CuCN is a poisonous reagent.
The effects of various solvents on the formation of 3a was also
investigated, and triethylamine was found to be the best solvent for the
reaction. We found the yield was very poor when reaction was carried out
in benzene or in DMF and triethylamine (V/V ¼ 5 mL/5 mL). There was no
reaction when benzene, CH Cl , CH CN (10 mL) was used as solvent and
2
2
3

ORDER
REPRINTS
TERMINAL ALKYNES AND AROYL CHLORIDES
3529
Table 1. Preparation of a,b-Conjugated Acetylenic Ketones 3a–i
a
b
c
Yield /%
ꢁ
ꢁ
Entry
Product
MP C/Lit MP C
9
3
3
3
3
3
3
3
3
3
a
b
c
d
e
f
g
h
i
C H COCꢂCC H
87
91
80
93
83
76
85
79
82
47–48/46–48
6
5
6
5
1
0
4-Cl-C
2-Cl-C
6
H
H
4
COCꢂCC
COCꢂCC
6
H
H
5
103–104/105
oil
6
4
6
5
1
1
4-Br-C H COCꢂCC H
106–107/110
1
6
4
6
5
2
2-Br-C
6
H
4
COCꢂCC
6
H
5
oil/oil
72–73/73.5–74
5
C
6
H
5
CH¼CH COCꢂCC
6 5
H
1
3
4-CH -C H COCꢂCC H
67–68/71
98–99/100
93–94/95
3
6
4
6
5
1
0
4-CH
3
O-C
H
6 4
COCꢂCC
6
H
5
1
3
a-Np COCꢂCC
6
H
5
a
b
Mole ratio: Phenylacetylene: aroyl chloride: CuI ¼ 2.5:3.2:0.25. The reaction were
N using CuI as catalyst at 525 W for 10 min under
argon atmostphere. Isolated yields.
carried out in the presence of Et
3
c
Table 2. Effect of the Catalyst on the Formation of 3a
Catalyst
Yield/%
Pd(PPh
3
)
2
Cl
2
-CuI
CuI
87
CuCN
85
CuBr
57
CuCl
trace
no
0
91
Table 3. Effect of the Power of Microwave Irradiation on the Formation of 3a
Power/W
Yield/%
375
62
450
75
525
87
600
83
675
78
750
56
Table 4. Effect of the Time of Microwave Irradiation on the Formation of 3a
Time/min
Yield/%
6
7
8
9
10
87
12
57
68
79
83
85.5
triethylamine, K CO , K PO as base. So we thought that triethylamine was
3
2
3
4
not only as solvent but also as base and ligand for the reaction.
We also studied the effects of power and time of microwave irradiation
for the formation of 3a. The results are summarized in Table 3 and Table 4.

ORDER
REPRINTS
3
530
WANG ET AL.
Table 5. Comparison of Times and Yields in Synthesis of Compounds 3a–i Using
Microwave and Conventional Heating
Conventional heating
Microwave heating
Product
T/h
Yield/%
P/W
T/min
Yield/%
c
t /tmw
3
3
3
3
3
3
3
3
3
a
b
c
d
e
f
g
h
i
30
30
30
30
30
36
30
30
30
78
80
67
81
69
52
76
65
61
525
525
525
525
525
525
525
525
525
10
10
10
10
10
10
10
10
10
87
91
80
93
83
76
85
79
82
180
180
180
180
180
216
180
180
180
The result show that the highest yield compound 3a can be obtained in
525 W for 10 min under microwave irradiation conditions.
The impact of the microwave irradiation and conventional heating for
synthesis of compound 3a–i have been compared and results are summar-
ized in Table 5. The result show that compounds 3a–i under microwave
irradiation were 180–216 times faster than under conventional heating.
The ratio between the reaction time using conventional reaction and micro-
wave irradiation (t /tmw) under the same condition, quantifies the microwave
c
heating effect.
EXPERIMENTAL
Infrared spectra were measured as KBr discs (or liquid film) using
1
an Alpha centauri FT-IR spectrometer. H NMR spectra (80 MHz)
were recorded in CDCl using a FT-80 spectrometer. Mass spectra were
3
obtained on a QP-1000A GC-MS spectrometer using the electron impact
mode (70 eV or 20 eV). Microwave irradiation was carried out with a
commercial microwave oven GlanzWP 750B at 2450 Hz. Melting points
were determined with an eletrothermal micromelting point apparatus and
are uncorrected.
General Procedure for the Preparation of Compounds 3a–i. A mixture
of aroyl chlorides (3.2 mmol), phenylacetylene (2.5 mmol), cuprous iodide
(0.125 mmol), triethylamine (10 mL) was irradiated at 525 W for 10 min by
microwave under argon atmosphere. The mixture was cooled to room

ORDER
REPRINTS
TERMINAL ALKYNES AND AROYL CHLORIDES
3531
temperature then methyl alcohol (5 mL) was added and the mixture was
stirred for 5 min. The solvent was removed under reduced pressure, diethyl
ether (20 mL) and water (20 mL) was added to residue, the aqueous layer
was extracted with diethyl ether (20 mL ꢃ 2), the organic extract was washed
with water (20 mL ꢃ 3), 5% H SO (20 mL ꢃ 3), saturated NaHCO
2
4
3
(
20 mL ꢃ 3), and brine (20 mL ꢃ 3) and then dried (magnesium sulfate).
The dried diethyl ether solution was concentrated, the product was purified
by column chromatography on silica gel (200–300 mesh) using petroleum
ꢁ
(
bp. 60–90 C)/ethyl acetate (v/v 10 : 1) as the eluent. All products have been
1
previously reported and were characterized by melting point, H NMR IR
and MS spectroscopy.
ACKNOWLEDGMENTS
We thank the National Natural Science Foundation of China and the
Northwest Normal University Science and Technology Development
Foundation of China for financial support.
REFERENCES
1
. (a) Adlington, R.M.; Baldwin, J.E.; Catterick, D.; Pritchard, G.J.;
Tang, L.T. J. Chem. Soc. Perkin Trans. (I) 2000, 303; (b) Ma, D.;
Lin, Y.; Lu, X.; Yu, Y. Tetrahedron Lett. 1988, 29, 1045; (c) Ma, D.;
Lu, X. Tetrahedron 1990, 46, 6319; (d) Negishi, E.; Kotora, M.
Tetrahedron 1997, 20, 6721.
2
. (a) Drewes, S.E.; Douglass, D.; Malissar, D.G.S.; Roos, G.H.P.;
Kaye, P.T. J. Chem. Soc. Perkin Trans. (I) 1990, 1507; (b) Kundu,
N.G.; Dasgupta, S.K. J. Chem. Soc. Perkin Trans. (I) 1993, 2657.
. (a) Normant, J.F. Synthesis 1972, 63; (b) Logue, M.W.; Moore, G.L.
J. Org. Chem. 1975, 40, 131; (c) Davis, R.B.; Scheiber, D.H. J. Am.
Chem. Soc. 1956, 78, 1675; (d) Bourgain, M.; Normant, J.F. Bull. Soc.
Chim. Fr. 1973, 2137; (e) Yashina, O.G.; Kaigorodova, T.D.; Zarva,
T.V.; Vereshchagin, L.I. Zh. Org. Khim. 1968, 4, 1904; (f) Yashina,
O.G.; Kaigorodova, T.D.; Zarva, T.V.; Vereshchagin, L.I. Zh. Org.
Khim. 1968, 4, 2104; (g) Compagnon, P.L.; Grosjean, B.; Lacour, M.
Bull. Soc. Chim. Fr. 1975, 779; (h) Yamaguchi, M.; Shibato, K.;
Fujuwara, S.; Hirao, I. Synthesis 1986, 421.
3
4
5
. Chowdhury, C.; Kundu, N.G. Tetrahedron Lett. 1996, 37, 7323.
. Tohda, Y.; Sonogashra, K.; Hagihara, N. Synthesis 1977, 777.

ORDER
REPRINTS
3
532
WANG ET AL.
6. (a) Loupy, A.; Petit, A.; Hamelin, J.; Texier-Boullet, F.; Jacquault, P.;
Mathe, D. Synthesis 1998, 1213; (b) Varma, R.S. Green Chem.
1
999, 43.
. Jin-Xian; Wang; Lin, Bai; Wenbo, Li.; Yulai, Hu. Synth. Commun.
000, 30, 325.
. Jin-Xian; Wang; Lin, Bai; Zhanxiang, Liu. Synth. Commun. 2000,
0, 971.
. Chopard, P.A.; Searle, R.J.G.; Devitt, F.R. J. Org. Chem. 1965,
0, 1015.
7
8
9
2
3
3
1
1
1
1
0. Duguay, G.; Quiniou, H. Bull. Soc. Chim. Fr. 1970, 1918.
1. Bickel, C.L. J. Am. Chem. Soc. 1947, 47, 2134.
2. Sashida, H. Synthesis 1998, 745.
3. Johnston, K.M.; Shotter, R.G. J. Chem. Soc. (c) 1967, 2476.
Received in the Netherlands January 8, 2001

Request Permission or Order Reprints Instantly!
Interested in copying and sharing this article? In most cases, U.S. Copyright
Law requires that you get permission from the article’s rightsholder before
using copyrighted content.
All information and materials found in this article, including but not limited
to text, trademarks, patents, logos, graphics and images (the "Materials"), are
the copyrighted works and other forms of intellectual property of Marcel
Dekker, Inc., or its licensors. All rights not expressly granted are reserved.
Get permission to lawfully reproduce and distribute the Materials or order
reprints quickly and painlessly. Simply click on the "Request
Permission/Reprints Here" link below and follow the instructions. Visit the
U.S. Copyright Office for information on Fair Use limitations of U.S.
copyright law. Please refer to The Association of American Publishers’
(AAP) website for guidelines on Fair Use in the Classroom.
The Materials are for your personal use only and cannot be reformatted,
reposted, resold or distributed by electronic means or otherwise without
permission from Marcel Dekker, Inc. Marcel Dekker, Inc. grants you the
limited right to display the Materials only on your personal computer or
personal wireless device, and to copy and download single copies of such
Materials provided that any copyright, trademark or other notice appearing
on such Materials is also retained by, displayed, copied or downloaded as
part of the Materials and is not removed or obscured, and provided you do
not edit, modify, alter or enhance the Materials. Please refer to our Website
User Agreement for more details.
Order now!
Reprints of this article can also be ordered at
http://www.dekker.com/servlet/product/DOI/101081SCC100106214