Microwave irradiated solventless Sonogashira reaction on nickel(0) powder doped KF/Al2O3

Article abstract of DOI:10.1081/SCC-200026232

A microwave irradiated solventless Sonogashira coupling reaction catalyzed by nanosize nickel(0) powder on potassium fluoride-alumina mixture has been developed. Terminal alkynes couple with aryl, alkenyl iodide, and aryl bromide in the presence of cuprou

Full text of DOI:10.1081/SCC-200026232

This article was downloaded by: [Georgetown University]
On: 05 September 2014, At: 03:30
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 Irradiated
Solventless Sonogashira
Reaction on Nickel(0) Powder
Doped KF/Al O
2
3
a
a
a b
Min Wang , Pinhua Li & Lei Wang
a
Department of Chemistry , Huaibei Coal Teachers
College , Huaibei, Anhui, 235000, P.R. China
b
State Key Laboratory of Organometallic
Chemistry, Shanghai Institute of Organic
Chemistry, Chinese Academy of Sciences ,
Shanghai, P.R. China
Published online: 10 Jan 2011.
To cite this article: Min Wang , Pinhua Li & Lei Wang (2004) Microwave Irradiated
Solventless Sonogashira Reaction on Nickel(0) Powder Doped KF/Al O , Synthetic
2
3
Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 34:15, 2803-2812, DOI: 10.1081/SCC-200026232
To link to this article: http://dx.doi.org/10.1081/SCC-200026232
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

w
SYNTHETIC COMMUNICATIONS
Vol. 34, No. 15, pp. 2803–2812, 2004
Microwave Irradiated Solventless
Sonogashira Reaction on Nickel(0)
Powder Doped KF/Al O3
2
1
Min Wang, Pinhua Li, and Lei Wang
1
1,2,*
1
Department of Chemistry, Huaibei Coal Teachers College,
Huaibei, Anhui, P.R. China
2
State Key Laboratory of Organometallic Chemistry,
Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, Shanghai, P.R. China
ABSTRACT
A microwave irradiated solventless Sonogashira coupling reaction cata-
lyzed by nanosize nickel(0) powder on potassium fluoride–alumina
mixture has been developed. Terminal alkynes couple with aryl,
alkenyl iodide, and aryl bromide in the presence of cuprous iodide, tri-
phenylphosphine, and ultrafine particle nickel(0) on potassium fluoride–
alumina to generate the corresponding cross-coupling products.
Key Words: Sonogashira reactions; Microwave irradiation; Nanosize
nickel(0) powder; Potassium fluoride–alumina; Solventless.
*
Correspondence: Lei Wang, Department of Chemistry, Huaibei Coal Teachers
College, Huaibei, Anhui 235000, P.R. China; Fax: 0086 561 3090518; E-mail:
leiwang@hbcnc.edu.cn.
2
803
DOI: 10.1081/SCC-200026232
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

2
804
Wang, Li, and Wang
INTRODUCTION
Transition metal-catalyzed cross-coupling reaction of organometallic
compounds with organic electrophiles is one of the most important tool for
[
1]
constructing carbon–carbon bonds.
palladium-catalyzed coupling of organic halides and pseudohalides with organo-
Generally, the most common is
[2]
[3]
[4]
[5]
boronic acids,
organostannanes,
6]
organozinc,
alkenes,
and aryl
[
Grignard reagent. The palladium-catalyzed coupling of terminal acetylenes
with aryl and vinyl halides (the Sonogashira reaction) is one of the important
[7]
and widely used tools for the preparation of alkynes. The Sonogashira reac-
tion generally proceeds in the presence of a homogeneous palladium catalyst
which makes the recovery of the metal tedious if not impossible and might
result in high palladium contamination of the product. Because of cheap avail-
[
8]
ability and high catalytic activity, Ni(0) has been used in Suzuki coupling,
[10]
[
9]
[11]
Negishi reaction, Kumada coupling,
and amination
in the last two
[12]
decades. To the best of our knowledge, there is a report on the Sonogashira
reaction catalyzed by Ni(PPh ) Cl in dioxane, but this approach is only
3
2
2
[
13]
limited to aromatic terminal alkynes.
nickel(0) powder catalyzed Sonogashira reaction in iso-propanol.
Recently we developed an ultrafine
[14]
Alumina is a particularly useful reagent in organic syntheses because it
can be modified in variety of ways which enhance its reactivity. It also obvi-
[
15]
ates a number of environmental problems.
irradiation of organic reactions has gained popularity since microwaves
In recent years, microwave
[16]
were found to accelerate a wide variety of transformations.
Early exper-
iments utilized solvents with high dielectric constants which permitted rapid
heating of reaction solutions. A number of reports have appeared in which
reactants are coated onto surfaces which themselves absorb little or no micro-
wave energy; in these instances, the reactive species absorb the microwave
energy but the temperature of the bulk reaction mixture tends to rise only
modestly. This results in relatively large energy saving as well as making it
possible to carry out reactions in relatively simple glasswares, such as open
[17]
beakers and flasks.
Here we wish to report a microwave irradiated nanosize activated
nickel(0) powder catalyzed Sonogashira reaction of terminal alkynes with
aryl and vinyl iodides and aryl bromides on potassium fluoride–alumina
under solvent free conditions (Sch. 1).
Table 1 lists the coupled results of a variety of terminal alkynes
with organic halides. Aromatic terminal alkynes and aliphatic terminal
alkynes were successfully coupled with aromatic, heteroaromatic, and vinyl
iodides in the presence of nanosize nickel(0) powder, cuprous iodide, and
triphenylphosphine doped on potassium fluoride–alumina mixture to
provide good yields of the corresponding cross-coupling products.

Sonogashira Reaction on Nickel(0) Powder
2805
Scheme 1.
However, aromatic bromides give moderate yields of the product because of
their low reactivity. Substituent effects in aromatic alkynes and aromatic
iodides were also examined. The results indicate that the reaction is relatively
insensitive to the electronic characteristics of a substituent as well as its
location.
During the investigation, we found that the reaction did not occur in the
absence of nickel(0) powder. The microwave reaction should not be attempted
in the absence of alumina which apparently acts as a temperature moderator.
Without alumina, the liquid reactants can react uncontrollably in the presence
of metallic nickel.
Since potassium fluoride is an effective desilylating reagent for trimethyl-
silyl-substituted acetylene, we use trimethylsilyl derivative of aryl terminal
alkynes as starting material to react with aromatic iodide in a one-pot Sono-
gashira reaction. 1-Phenyl-2-(trimethylsilyl)acetylene coupled with p-iodo-
toluene to generate the corresponding cross-coupling product in good yield
(83%) under the reaction conditions (Sch. 2).
In conclusion, a novel procedure for the synthesis of arylacetylenes
via the Sonogashira coupling reaction was developed, which involves the
use of nanosize activated nickel(0) powder as catalyst under microwave
irradiation and solvent free conditions. The reaction is an inexpensive
alternative to the palladium-catalyzed process, and results in good yields of
the desired product.
EXPERIMENTAL
Melting points were recorded on a WRS-1B melting point apparatus and
1
are uncorrected. All H NMR spectra were recorded on a 60 MHz JEOL MY
6
0 FT-NMR or a 250 MHz or a 400 MHz Bruker spectrometer. Chemical shift
are given as d value with reference to tetramethylsilane (TMS) as internal
standard. IR spectra were obtained by using a Nicolet NEXUS 470 spectro-
photometer. GC/MS data were obtained by using a Hewlett-Packard 6890
series GC equipped with a 5983 mass selective detector. The reagents were
received from commercial supply without purification prior to use. Products
were purified by flash column chromatography.

2
806
Wang, Li, and Wang

Sonogashira Reaction on Nickel(0) Powder
2807
Scheme 2.
General Procedure for the Reaction
The synthesis of diphenylacetylene is representative. Iodobenzene (204 mg,
.00 mmol) and phenylacetylene (107 mg, 1.05 mmol) were added to a mixture
1
of KF/Al O (1.00 g, 40% by weight), nickel(0) powder (15 mg, 0.25mmol,
2
3
9
9.9þ% as a nanosize activated powder), cuprous iodide (35mg, 0.18mmol),
and triphenylphosphine (157mg, 0.60mmol) contained in a clean, dry, 25-mL
round-bottomed flask. The mixture was stirred at room temperature to ensure
efficient mixing. The flask was then fitted with a septum (punctured by an 18
gauge needle), placed in the microwave and irradiated at 30% power for
9
min. (Caution: the reactions were halted at the half way point to allow mixtures
to cool for safe and efficient purposes and heating volatile materials in
commercial microwave ovens for extended periods can be hazardous.) After
cooling, hexane (5 mL) was added and the slurry stirred at room temperature
to ensure product removal from the surface. The mixture was vacuum
filtered using a sintered glass funnel and the product was purified by flash
chromatography to yield 0.160 g of diphenylacetylene (90% yield).
[
18] 1
1
-Phenyl-1-decyne. Oil;
H NMR (CDCl ) d 7.41–7.38 (m, 2H),
3
7
1
1
.29–7.26 (m, 3H), 2.36 (t, J ¼ 6.96 Hz, 2H), 1.64–1.52 (m, 2H), 1.45–
1
3
.32 (m, 10 H), 0.88 (t, J ¼ 6.44 Hz, 3H); C NMR (CDCl ) d 131.4,
3
28.1, 127.4, 124.2, 90.2, 80.5, 31.8, 29.2, 29.1, 28.9, 28.8, 22.8, 19.3, 14.0;
þ
MS m/z (%) 214 (M , 11), 171 (3), 157 (20), 143 (55), 129 (69), 115
(
100), 91 (41).
-(4-Methylphenyl)-1-decyne. Oil;
d, J ¼ 7.92 Hz, 2H), 7.14 (d, J ¼ 7.51 Hz, 2H), 2.35 (t, J ¼ 7.64 Hz, 2H),
[
19]
1
1
H NMR (CDCl ) d 7.32
3
(
2
3
2
1
.32 (s, 3H), 1.62–1.55 (m, 2H), 1.43–1.29 (m, 10 H), 0.89 (t, J ¼ 6.47 Hz,
1
H); C NMR (CDCl ) d 137.1, 131.5, 128.7, 121.0, 89.4, 80.5, 31.9, 29.2,
3
3
þ
9.1, 28.9, 28.8, 22.9, 21.3, 19.4, 14.1; MS m/z (%) 228 (M , 19), 185 (4),
71 (10), 157 (32), 143 (35), 131 (100), 115 (20), 91 (14).
[
20] 1
1
-Phenyl-1-octyne. Oil;
H NMR (CDCl ) d 7.40–7.35 (m, 2H),
3
7
1
1
2
.29–7.22 (m, 3H), 2.35 (t, J ¼ 6.91 Hz, 2H), 1.68–1.57 (m, 2H), 1.50–
1
3
.39 (m, 6 H), 0.89 (t, J ¼ 6.70 Hz, 3H); C NMR (CDCl ) d 131.6, 128.0,
3
þ
27.4, 124.1, 90.3, 80.6, 31.6, 28.8, 22.7, 19.4, 14.1; MS m/z (%) 186 (M ,
3), 157 (18), 143 (59), 129 (60), 115 (100), 91 (35).
[19]
1
Phenyl-p-tolylacetylene. MP 72–738C (lit.
71–738C); H NMR
(
(
CDCl ) d 7.50–7.45 (m, 2H), 7.40 (d, J ¼ 7.80 Hz, 2H), 7.26–7.22
3
1
3
m, 3H), 7.14 (d, J ¼ 7.82 Hz, 2H), 2.31 (s, 3H); C NMR (CDCl ) d
3

2
808
Wang, Li, and Wang
1
38.3, 131.5, 129.0, 128.2, 123.4, 120.2, 89.6, 88.7, 21.4; MS m/z (%) 192
þ
(
M , 100), 165 (15), 139 (4), 115 (6), 94 (10).
[19]
1
H NMR (CDCl ) d 7.50–7.42 (m, 4H), 7.35–7.31 (m, 5H); C NMR
-(4-Bromophenyl)phenylacetylene. MP 83–848C (lit.
82–848C);
13
1
3
(
CDCl ) d 133.0, 131.6, 128.5, 128.4, 122.9, 122.5, 122.2, 90.5, 88.3; MS
3
þ
m/z (%) 258, 256 (M , 97, 100), 176 (88), 151 (37), 128 (17), 88 (61).
[19]
1
-(4-Acetylphenyl)phenylacetylene. MP 95–978C (lit.
95–968C);
1
H NMR (CDCl ) d 7.90 (d, J ¼ 8.40 Hz, 2H), 7.63 (d, J ¼ 8.44 Hz, 2H),
3
1
.53–7.48 (m, 2H), 7.35–7.30 (m, 3H), 2.62 (s, 3H); C NMR (CDCl ) d
3
7
1
2
8
3
97.1, 136.0, 131.7, 131.6, 128.6, 128.4, 128.2, 128.1, 122.7, 92.6, 88.7,
þ
6.5; MS m/z (%) 220 (M , 62), 205 (100), 176 (51), 151 (21), 102 (11),
8 (22).
[
19] 1
1
-(4-Methoxylphenyl)-1-decyne. Oil;
H NMR (CDCl ) d 7.30
3
(
(
(
d, J ¼ 8.72 Hz, 2H), 6.92 (d, J ¼ 8.74 Hz, 2H), 3.74 (s, 3H), 2.38
t, J ¼ 7.01 Hz, 2H), 1.67–1.58 (m, 2H), 1.45–1.29 (m, 10 H), 0.89
1
3
t, J ¼ 6.05 Hz, 3H); C NMR (CDCl ) d 159.1, 132.9, 116.4, 113.9, 88.8,
3
þ
8
0.2, 55.2, 31.8, 29.2, 29.1, 28.9, 22.2, 19.4, 14.1; MS m/z (%) 244 (M ,
1
9), 201 (5), 188 (24), 173 (30), 159 (31), 147 (100), 121 (35), 115 (20), 91
14).
(
1
1
-(4-Acetylphenyl)-1-decyne. Oil; H NMR (CDCl ) d 7.85 (m, 2H),
3
7
.37 (m, 2H), 2.55 (s, 3H), 2.42 (t, J ¼ 7.21 Hz, 2H), 1.61–1.59 (m, 2H),
1
3
1
NMR (CDCl ) d 197.2, 135.7, 131.7, 129.2, 128.2, 94.4, 80.2, 31.9, 29.2,
.44–1.42 (m, 2H), 1.34–1.29 (m, 8H), 0.89 (t, J ¼ 5.21 Hz, 3H);
C
3
2
H, 9.44. Found: C, 84.47; H, 9.36. HRMS (EI) calcd for C H O
9.1, 29.0, 28.6, 26.5, 22.7, 19.6, 14.1. Anal. Calcd for C H O: C, 84.32;
18 24
1
8
24
2
56.1827, found: 256.1836.
-(4-Nitrophenyl)phenylacetylene. MP 120–1218C (lit.
[
19]
1
120–
1
1
228C); H NMR (CDCl ) d 8.20 (d, J ¼ 8.80 Hz, 2H), 7.68 (d, J ¼ 8.76 Hz,
3
1
H), 7.56–7.50 (m, 2H), 7.38–7.34 (m, 3H), 2.60 (s, 3H); C NMR (CDCl )
3
2
d 146.8, 132.2, 131.7, 130.2, 129.2, 128.4, 123.6, 122.0, 94.7, 87.5; MS m/z
3
þ
(
%) 223 (M , 100), 193 (42), 176 (80), 165 (31), 151 (44), 139 (10), 126 (15).
[
21]
1
Diphenylacetylene. MP 59–618C (lit.
d 7.56–7.51 (m, 4H), 7.34–7.30 (m, 6H); C NMR (CDCl ) d 131.5, 128.2,
60–628C); H NMR (CDCl )
3
1
3
3
þ
1
28.1, 123.2, 89.2; MS m/z (%) 178 (M , 100), 152 (20), 126 (9), 89 (15).
[
19]
1
2
CDCl ) d 7.52–7.45 (m, 2H), 7.32–7.22 (m, 5H), 6.99–6.94 (m, 1H);
-Phenylethynylthiophene. 51–538C (lit.
51–538C); H NMR
13
(
C
NMR (CDCl ) d 131.9, 131.5, 128.3, 127.1, 127.0, 123.4, 122.9, 93.1, 82.6;
3
3
þ
MS m/z (%) 184 (M , 100), 152 (20), 139 (20), 92 (10).
[
19] 1
7
-Chloro-1-phenyl-3-hepten-1-yne. Oil;
H NMR (CDCl ) d 7.45–
3
7
1
.41 (m, 2H), 7.32–7.25 (m, 3H), 6.24–6.11 (m, 1H), 5.76 (d, J ¼ 16.90 Hz,
1
3
H), 3.51 (t, J ¼ 6.85 Hz, 2H), 2.36–2.26 (m, 2H), 1.93–1.82 (m, 2H);
C
NMR (CDCl ) d 142.5, 131.5, 128.1, 128.0, 123.3, 111.0, 88.5, 87.8, 44.1,
3

Sonogashira Reaction on Nickel(0) Powder
2809
þ
3
1.5, 30.1; MS m/z (%) 206, 204 (M , 16, 50), 155 (60), 141 (100), 128 (24),
1
15 (76), 91 (20).
ACKNOWLEDGMENTS
We wish to thank the National Natural Science Foundation of China (No.
0372024, 20172018), the Excellent Scientist Foundation of Anhui Province,
2
China (No. 2001040), the Natural Science Foundation of the Education
Department of Anhui Province, China (No. 2002kj254zd), the Scientific
Research Foundation for the Returned Overseas Chinese Scholars, State
Education Ministry, China (No. 2002247), and the Excellent Young Teachers
Program of MOE, China (No. 2024) for financial support.
REFERENCES
1
2
. (a) Tamao, K. Comprehensive Organic Synthesis; Trost, B.M.,
Fleming, L., Eds.; Pergamon Press: Elmsford, NY, 1991; Vol. 3,
4
35–480; (b) Knight, D.W. Comprehensive Organic Synthesis;
Trost, B.M., Fleming, L., Eds.; Pergamon Press: Elmsford, NY, 1991;
Vol. 3, 481–520.
. (a) Miyaura, N.; Suzuki, A. Palladium-catalyzed cross-coupling reactions
of organoboron compounds. Chem. Rev. 1995, 95 (7), 2457–2483;
(b) Suzuki, A. Recent advances in the cross-coupling reactions of organo-
boron derivatives with organic electrophiles, 1995–1998. J. Organomet.
Chem. 1999, 576 (1–2), 147–168.
3
4
. Stille, J.K. The palladium-catalyzed cross-coupling reactions of organotin
reagents with organic electrophiles [new synthetic methods (58)]. Angew.
Chem. Int. Ed. Engl. 1986, 25 (6), 508–524.
. (a) Negishi, E.-i.; King, A.O.; Okukado, N. Selective carbon–carbon
bond formation via transition metal catalysis. 3. A highly selective
synthesis of unsymmetrical biaryls and diarylmethanes by the nickel- or
palladium-catalyzed reaction of aryl- and benzylzinc derivatives with
aryl halides. J. Org. Chem. 1977, 42 (10), 1821–1823; (b) Negishi, E.-i.
Palladium- or nickel-catalyzed cross coupling. A new selective method
for carbon–carbon bond formation. Acc. Chem. Res. 1982, 15 (11),
340–348; (c) Erdik, E. Organozinc Reagents in Organic Synthesis;
CRC Press: Boca Raton, FL, 1996; 271–334.
5
. Dieck, H.A.; Heck, R.F. Organophosphinepalladium complexes as cata-
lysts for vinylic hydrogen substitution reactions. J. Am. Chem. Soc.
1
974, 96 (4), 1133–1136.

2
810
Wang, Li, and Wang
6
. (a) Hayashi, T.; Konishi, M.; Kobori, Y.; Kumada, M.; Higuchi, T.;
0
Hirotsu, K. Dichloro[1,1 -bis(diphenylphosphino)ferrocene]palladiu-
m(II): an effective catalyst for cross-coupling of secondary and primary
alkyl Grignard and alkylzinc reagents with organic halides. J. Am.
Chem. Soc. 1984, 106 (1), 158–163; (b) Tamao, K.; Kumada, M. The
Chemistry of the Metal-Carbon Bond; Hartley, F.R., Ed.; Wiley:
New York, 1987; Vol. 4, 819.
7
. (a) Sonogashira, K.; Tohda, Y.; Hagihara, N. A convenient synthesis of
acetylenes: catalytic substitutions of acetylenic hydrogen with bromo-
alkenes, iodoarenes and bromopyridines. Tetrahedron Lett. 1975,
1
6 (50), 4467–4470; (b) Tohda, Y.; Sonogashira, K.; Hagihara, N.
Novel insertion of acetylene into s-alkynyl palladium complexes.
J. Chem. Soc. Chem. Commun. 1975, (2), 54–55; (c) Jones, G.B.;
Wright, J.M.; Ploured, G.W.; Hynd, G.; Huber, R.S.; Mathews, J.E. A
direct and stereocontrolled route to conjugated enediynes. J. Am.
Chem. Soc. 2000, 122 (9), 1937–1944; (d) Liu, S.-X.; Michel, C.;
Schmittel, M. A highly regioselective Sonogashira coupling as a key
step in the preparation of the first phenanthroline with two diverse reac-
tive groups in 3,8-positions. Org. Lett. 2000, 2 (25), 3959–3962;
(
e) Shen, W.; Thomas, S.A. Synthesis of 1,3-diynes via palladium-cata-
lyzed reaction of 1,1-dibromo-1-alkenes. Org. Lett. 2000, 2 (18),
857–2860; (f) Kabalka, G.W.; Wang, L.; Namboodiri, V.; Pagni, R.M.
2
Rapid microwave-enhanced, solventless Sonogashira coupling reaction
on alumina. Tetrahedron Lett. 2000, 41 (27), 5151–5154.
8
. (a) Lipshutz, B.H.; Sclafani, J.A.; Blomgren, P.A. Biaryls via Suzuki
cross-coupling catalyzed by nickel on charcoal. Tetrahedron 2000,
56 (15), 2139–2144; (b) Saito, S.; Ohtani, S.; Miyaura, N. Synthesis of
biaryls via a nickel(0)-catalyzed cross-coupling reaction of chloroarenes
with arylboronic acids. J. Org. Chem. 1997, 62 (23), 8024–8030;
(c) Percec, V.; Bae, J.-Y.; Hill, D.H. Aryl mesylates in metal-catalyzed
homocoupling and cross-coupling reactions. 2. Suzuki-type nickel-
catalyzed cross-coupling of aryl arenessulfonates and aryl mesylates
with arylboronic acids. J. Org. Chem. 1995, 60 (4), 1060–1065.
. Lipshutz, B.H.; Blomgren, P.A. Nickel on charcoal (“Ni/C”): an expedi-
ent and inexpensive heterogeneous catalyst for cross-coupling between
aryl chlorides and organometallics. I. Functionalized organozinc reagents.
J. Am. Chem. Soc. 1999, 121 (24), 5819–5820.
9
1
0. Lipshutz, B.H.; Tomioka, T.; Blomgren, P.A.; Sclafani, J.A. Kumada
coupling catalyzed by nickel on charcoal (Ni/C). Inorg. Chim. Acta
1
999, 296 (1), 164–169.
1
1. Lipshutz, B.H.; Ueda, H. Aromatic aminations by heterogeneous Ni(0)/C
catalysis. Angew. Chem. Int. Ed. 2000, 39 (24), 4492–4493.

Sonogashira Reaction on Nickel(0) Powder
2811
12. (a) Lipshutz, B.H.; Tasler, S.; Chrisman, W.; Spliethoff, B.; Tesche, B. On
the nature of the “heterogeneous” catalyst: nickel-on-charcoal. J. Org.
Chem. 2003, 68 (4), 1177–1189; (b) Rayabarapu, D.K.; Cheng, C.-H.
Synthesis of seven-membered lactones via nickel- and zinc-catalyzed
highly regio- and stereoselective cyclization of 2-iodobenzyl alcohols
with propiolates. J. Am. Chem. Soc. 2002, 124 (20), 5630–5631;
(c) Spielvogel, D.J.; Buchwald, S.L. Nickel-BINAP catalyzed enantio-
selective a-arylation of a-substituted g-butyrolactones. J. Am. Chem.
Soc. 2002, 124 (14), 3500–3501.
1
3. Beletskaya, I.P.; Latyshev, G.V.; Tsvetkov, A.V.; Lukashev, N.V. The
nickel-catalyzed Sonogashira-Hagihara reaction. Tetrahedron Lett.
2
003, 44 (27), 5011–5013.
4. Wang, L.; Li, P.; Zhang, Y. The Sonogashira coupling reaction catalyzed
1
1
1
by nanoparticle nickel(0). Chem. Commun. 2004, (5), 514–515.
5. Kabalka, G.W.; Pagni, R.M. Organic reactions on alumina. Tetrahedron
1997, 53 (24), 7999–8065 and references cited therein.
6. (a) Kabalka, G.W.; Pagni, R.M.; Hair, C.M. Solventless Suzuki coupling
reactions on palladium-doped KF/Al O . Org. Lett. 1999, 1 (9),
3
2
1423–1425; (b) Kabalka, G.W.; Pagni, R.M.; Wang, L.; Namboodiri, V.;
Hair, C.M. Microwave-assisted, solventless suzuki coupling reaction on
palladium-doped alumina. Green Chem. 2000, 2 (3), 120–122;
(c) Kabalka, G.W.; Wang, L.; Pagni, R.M. A novel route to 2-(dialkylami-
nomethyl)benzo[b]furans via a microwave-enhanced, solventless mannich
condensation-cyclization on cuprous iodide doped alumina. Tetrahedron
Lett. 2001, 42 (35), 6049–6051; (d) Kabalka, G.W.; Wang, L.;
Pagni, R.M. Microwave enhanced Glaser coupling under solvent free con-
ditions. Synlett 2001, (1), 108–110; (e) Kabalka, G.W.; Wang, L.;
Pagni, R.M. A microwave-enhanced, solventless Mannich condensation
on Cui-doped alumina. Synlett 2001, (5), 676–678.
1
7. (a) Abramovitch, R.A. Application of microwave-energy in organic
chemistry. A review. Org. Prep. Proc. Int. 1991, 23 (6), 685–711;
(
b) Blettner, C.G.; Konig, W.A.; Stenzel, W.; Schotten, T. Microwave-
assisted aqueous Suzuki cross-coupling reactions. J. Org. Chem. 1999,
4 (11), 3885–3890; (c) Bose, D.S.; Jayalakshmi, B. Reagents for
6
organic synthesis: use of organostannyl oxides as catalytic neutral agents
in the preparation of nitriles from primary amides under microwave
irradiation. J. Org. Chem. 1999, 64 (5), 1713–1714; (d) Varma, R.S.
Solvent-free organic syntheses. Using supported reagents and microwave
irradiation. Green Chem. 1999, 1 (1), 43–55.
1
8. Sato, H.; Isono, N.; Miyoshi, I.; Mori, M. 1,1-, 1,2-, and 1,4-Eliminations
from the corresponding dihalogenated compounds using Bu SnSiMe -
2
F . Tetrahedron 1996, 52 (24), 8143–8158.
3
3

2
812
Wang, Li, and Wang
1
2
2
9. Kabalka, G.W.; Wang, L.; Pagni, R.M. Sonogashira coupling and cycliza-
tion reactions on alumina: a route to aryl alkynes, 2-substituted-benzo[b]-
furans and 2-substituted-indoles. Tetrahedron 2001, 57 (38), 8017–8028.
0. Masuda, Y.; Hoshi, M.; Arase, A. Reaction of trialkylborane with
1
-alkyne and lead(IV) acetate. A new regiospecific and stereospecific
one-pot synthesis of enol acetates. Chem. Lett. 1980, (4), 413–416.
1. Carpino, L.A.; Chen, H.W. Diphenylthiirene 1-oxide. Synthesis charac-
terization, and reactivity. J. Am. Chem. Soc. 1979, 101 (2), 390–394.
Received in Poland March 31, 2004