A convenient synthetic method of β-bromo alkenyl phenyl selenides by the reaction of alkynes with diphenyl diselenide and copper(II) bromide

Article abstract of DOI:10.1080/10426501003772177

When alkynes were allowed to react with diphenyl diselenide in the presence of copper(II) bromide, bromophenylselenation of the carbon-carbon triple bond smoothly proceeded to give the corresponding -bromo alkenyl phenyl selenides in moderate to good yields. Similarly, chlorophenylselenation of alkynes occurred by the use of copper(II) chloride as a copper salt giving β-chloro alkenyl phenyl selenides in good yields. Copyright Taylor & Francis Group.

Full text of DOI:10.1080/10426501003772177

This article was downloaded by: [Baskent Universitesi]
On: 21 December 2014, At: 19:51
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
Phosphorus, Sulfur, and Silicon and the
Related Elements
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gpss20
A Convenient Synthetic Method of β-
Bromo Alkenyl Phenyl Selenides by
the Reaction of Alkynes with Diphenyl
Diselenide and Copper(II) Bromide
Yutaka Nishiyama a , Haruko Ohnishi a , Masako Iwamoto a & Noboru
Sonoda a
a Department of Applied Chemistry, Faculty of Engineering , Kansai
University , Osaka, Japan
Published online: 27 May 2010.
To cite this article: Yutaka Nishiyama , Haruko Ohnishi , Masako Iwamoto & Noboru Sonoda (2010) A
Convenient Synthetic Method of β-Bromo Alkenyl Phenyl Selenides by the Reaction of Alkynes with
Diphenyl Diselenide and Copper(II) Bromide, Phosphorus, Sulfur, and Silicon and the Related Elements,
185:5-6, 1021-1024, DOI: 10.1080/10426501003772177
To link to this article: http://dx.doi.org/10.1080/10426501003772177
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

Phosphorus, Sulfur, and Silicon, 185:1021–1024, 2010
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426501003772177
A CONVENIENT SYNTHETIC METHOD OF β-BROMO
ALKENYL PHENYL SELENIDES BY THE REACTION OF
ALKYNES WITH DIPHENYL DISELENIDE AND COPPER(II)
BROMIDE
Yutaka Nishiyama, Haruko Ohnishi, Masako Iwamoto,
and Noboru Sonoda
Department of Applied Chemistry, Faculty of Engineering, Kansai University,
Osaka, Japan
When alkynes were allowed to react with diphenyl diselenide in the presence of copper(II)
bromide, bromophenylselenation of the carbon–carbon triple bond smoothly proceeded to
give the corresponding β-bromo alkenyl phenyl selenides in moderate to good yields. Sim-
ilarly, chlorophenylselenation of alkynes occurred by the use of copper(II) chloride as a
copper salt giving β-chloro alkenyl phenyl selenides in good yields.
Keywords Alkyne; copper(II) bromide; diphenyl diselenide
INTRODUCTION
β-Halo alkenyl phenyl selenides such as β-chloro and β-bromo alkenyl phenyl se-
lenides have been useful intermediates in organic synthesis.1 Then, there have been some
reports on the synthesis of β-halo alkenyl phenylselenides.2 The addition of phenyse-
lenenyl halides, such as phenylselenyl chloride (PhSeCl) and bromide (PhSeBr), to the
carbon–carbon triple bond of alkynes is the one of the direct synthetic methods of β-halo
alkenyl phenyl selenides (2a–e, 2g, and 2h). However, there are some disadvantages to the
preparation and utilization of phenylselenyl halides: (i) low humidity conditions, (ii) the
handling of chlorine and bromine, (iii) the use of phenylselnocyanate, and (iv) the formation
of phenylselnenyl trihalides as byproducts.3 As an approach to solve these problems, we
investigated another generation method of phenyselenenyl halides and found that the treat-
ment of dipehnyl diselenide copper(II) bromide and chloride is a useful in situ generation
method of phenyselenenyl halides (Scheme 1).
Received 29 November 2008; accepted 1 January 2009.
Dedicated to Professor Naomichi Furukawa on the occasion of his 70th birthday.
This research was supported by a Grant-in-Aid for Science Research (No.18550100), Research and Devel-
opment Organization of Industry-University Cooperation from the Ministry of Education, Culture, Sports, Science
and Technology of Japan and Kansai University Grant-in-Aid for progress of research in graduate course, 2007.
Address correspondence to Yutaka Nishiyama, Department of Applied Chemistry, Faculty of Engineering,
Kansai University, Suita, Osaka 564-8680, Japan. E-mail: nishiya@kansai-u.ac.jp
1021

1022
Y. NISHIYAMA ET AL.
R1
X
SePh
R2
CuX2
R1
R2
PhSeSePh
Scheme 1
RESULTS AND DISCUSSION
When phenylacetylene (1) was allowed to react with diphenyl diselenide (2) in the
presence of copper(II) bromide in toluene solution at 25◦C for 3 h under an atmosphere of air,
bromophenylselenation of the carbon–carbon triple bond of 1 smoothly proceeded to give
(E)-2-bromo-2-phenyl-1-phenylselenoethylene (3), which was an anti-addition product, in
88% yield along with the formation of small amount of regioisomers, 2-bromo-1-phenyl-
1-phenyselenoethylene (4) (5%) (see entry 1 in Table I). To know the optimized reaction
conditions, 1 was treated with 2 and copper(II) bromide under various reaction conditions,
and these results were shown in Table I. Even when hexane, acetic acid, and acetonitrile were
used as solvents, the addition products were formed in good yields; however, regioselectivity
of the products was slightly decreased (Table I, entries 2–4). At lower reaction temperature
(0◦C), the yields of bromophenylselenation products were improved by the extending of
the reaction time (15 h) (Table I, entries 5 and 6). The yield of 4 was also affected by the
ratios of copper(II) bromide used (Table I, entries 8 and 9). The results have shown that both
bromine atoms on copper(II) bromide were not introduced on the products. In contrast, it
is interesting to note that both phenylseleno groups on diphenyl diselenide were efficiently
utilized in the reaction (Table I, entry 9).4,5
A variety of alkynes were allowed to react with diphenyl diselenide and copper
(II) bromide, and these results are shown in Table II.6 The treatment of terminal alkyne,
which was substituted with an alkyl group, gave the corresponding bromophenylselenated
Table I Reaction of phenylacetylene with diphenyl diselenide in the presence of CuBr2
Ph
Br
SePh
H
Ph
Br
H
CuBr2
PhSeSePh
PhC CH
solv. (3.0 mL)
PhSe
1
2
0.3 mmol
3
4
Yield (%)a
Entry
1 (mmol)
2 (mmol)
Solv.
Temp. (◦C)
Time (h)
3
4
1
2
3
4
5
6
7
8
9b
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.6
0.6
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
C6H5CH3
C6H14
CH3COOH
CH3CN
C6H5CH3
C6H5CH3
C6H5CH3
C6H5CH3
C6H5CH3
25
25
25
25
0
3
3
3
3
3
15
1
3
88
68
73
60
13
62
37
35
75
5
13
18
27
3
7
3
11
24
0
25
25
25
3
aGC yield based on 1.
bCuBr2 (0.6 mmol) was used.

SYNTHESIS OF ALKENYL PHENYL SELENIDES
1023
a
Table II Reaction of alkynes with diphenyl diselenide and CuBr2
R1
Br
SePh
R2
R1
Br
CuBr2
PhSeSePh
R1
R2
solvent
25 °C, 3 h
PhSe
R2
5
6
Yield (%)b
Entry
R1
R2
Solvent
5
6
1
2
3
4
5
6
Ph
H
Ph
H
H
n-C4H9
C2H5
COCH3
COOC2H5
H
C6H5CH3
CH3CN
C6H5CH3
CH3COOH
CH3COOH
C6H5CH3
88
89
84
89
72
72
5
5
3
0
0
H
c-C6H9
22
aReaction conditions: alkyne (0.6 mmol), PhSeSePh (0.3 mmol), CuBr2 (0.6 mmol) and solvent (3.0 mL) at
25◦C for 3 h.
bGC yield based on alkyne.
products, (E)-1-bromo-2-phenylseleno-1-hexene, in 89% yield with highly regioselectivity
(Table II, entry 2). When alkynes bearing electron-withdrawing groups, such as but-3-yn-
2-one and ethyl propiolate, were allowed to react with diphenyl diselenide in the presence
of copper(II) bromide, β-bromo alkenyl phenyl selenides, in which the phenylseleno group
was introduced on the α-carbon of the starting materials, were formed in 89% and 72%
yields, respectively (Table II, entries 4 and 5).7 The use of unsymmetrical 1,2-disubstituted
alkyne also gave the addition products in 84% yield (Table II, entry 3). In the case of
1-ethynyl-cyclohex-1-ene, which has both carbon–carbon double and triple bonds, bro-
mophenylselenation of the carbon–carbon triple bond occurred with selectivity to afford
the mixture of 2-bromo-2-cyclohexenyl-1-phenylseleno ethylene (72%) and 2-bromo-1-
cyclohexenyl-1-phenylseleno ethylene (22%) (Table II, entry 6).
Next, to investigate the application of the reaction, we examined the chlorophenylse-
lenation of alkynes with diphenyl diselenide and copper chloride. When the reaction was
carried out at 80◦C, chlorophenylselenation of alkynes proceeded smoothly to give the
corresponding β-chloro alkenyl phenyl selenides in good yields (Scheme 2).
Ph
Cl
SePh
H
Ph
Cl
H
CuCl2
PhSeSePh
0.3 mmol
PhC CH
0.3 mmol
Toluene (3.0 mL)
80 °C, 3 h
PhSe
0.3 mmol
94 %
6 %
C4H9
SePh
C4H9
PhSe
Cl
H
CuCl2
PhSeSePh
0.3 mmol
C4H9C CH
0.3 mmol
CH3CN (3.0 mL)
80 °C, 3 h
H
Cl
71 %
12 %
0.3 mmol
Scheme 2
We cannot explain the reaction pathway in detail, but it was suggested that the
formation of episelenium ion (7) was the first step in the reaction. The halogen ion (Br−
or Cl−) attacked the 7 from the less hindered side to form anti-addition product. But in the

1024
Y. NISHIYAMA ET AL.
case of 1-hexyne, the ring opening of 7 predominantly proceeded to form the vinyl cation
intermediate (8). Then 8 reacted with the bromine anion to give the corresponding addition
product. Therefore, the stability of 8 played an important role on the regioselectivity.
We find a new synthetic method of β-bromo and β-chloro alkenyl phenyl selenides
by the reaction of alkynes with diphenyl diselenide and copper(II) bromide and chloride.
The halogen atom on the copper (II) halide and both phenylseleno groups on the diphenyl
diselenide are efficiently used in the reaction. The application of the reaction in organic
synthesis is now progress.
EXPERIMENTAL
A toluene (3.0 mL) solution of diphenyl diselenide (0.3 mmol), alkyne (0.6 mmol),
and CuBr2 (0.6 mmol) was stirred at 25◦C for 3 h under air. After the reaction, the resulting
solution was extracted with ether (10 mL × 3). The organic layer was dried over MgSO4
and filtered. The organic solvent was removed under reduced pressure. Purification of the
residue by HPLC afforded the corresponding β-bromo alkenyl phenyl selenide.
REFERENCES
1. (a) C. Paulmier, Selenium Reagents and Intermediates in Organic Synthesis (Pergamon Press, New
York, 1986); (b) S. Patai and Z. Rappoport, The Chemistry of Organic Selenium and Tellurium
Compounds (Wiley, New York, 1986), Vols. 1 and 2; (c) A. Krief and L. Hevesi, Organoselenium
Chemistry (Springer-Verlag, Berlin, 1988); (d) A. Krief, In Comprehensive Organic Synthesis, B.
M. Trost, ed. (Pergamon Press, Oxford, 1991), vol. 3; (e) T. G. Back, Organoselenium Chemistry,
Practical Approach (Oxford University Press, Oxford, UK, 1999).
2. (a) E. G. Kataev and T. G. Mannafov, Zh. Organ. Khim., 6, 1959 (1970); (b) E. G. Kataev, T. G.
Mannafov, and O. O. Saidov, Zh. Organ. Khim., 7, 2229 (1971); (c) E. G. Kataev, T. G. Mannafov,
and Y. Y. Samitov, Zh. Organ. Khim., 11, 2324 (1975); (d) C. N. Filer, D. Ahern, R. Fazio, and
E. J. Shelton, J. Org. Chem., 45, 1313 (1980); (e) D. G. Garratt, P. L. Beaulieu, and V. M. Morisset,
Can. J. Chem., 59, 927 (1981); (f) S. Tomoda, Y. Takeuchi, and Y. Nomura, Chem. Lett., 1715
(1981). (g) A. J. Bridges and J. W. Fischer, Tetrahedron Lett., 24, 445 (1983); (h) A. J. Bridges
and J. W. Fischer, J. Org. Chem., 49, 2954 (1984); (i) R. L. Antipin, E. K. Beloglazkina, and
N. V. Zyk, Khimiya, 47, 359 (2006).
3. (a) O. Behaghel and H. Seibert, Ber., 66, 708 (1933); (b) O. Behaghel and W. Muller, Ber., 67,
105 (1934); (c) H. J. Bridger and R. W. Pittman, J. Chem. Soc., 1371 (1950); (d) M. Renson and
J. L. Piette, Bull. Soc. Chim. Belg., 73, 507 (1964); (e) H. J. Reich, J. M. Renga, and I. L. Reich,
J. Am. Chem. Soc., 97, 5434 (1975); (f) A. Arase and Y. Masuda, Chem. Lett., 1115 (1976); (g) H.
J. Reich, M. L. Cohen, and P. D. Clark, Org. Synth., 59, 141 (1979).
4. Recently, Taniguchi have reported the copper-catalyzed synthesis of β-halo alkenyl sulfides by
the addition of disulfides to alkynes.5 Then, we examined the reaction of phenylacetylene with
diphenyl diselenide in the presence of CuBr; however, the reaction did not occur and starting
materials were recovered.
5. N. Taniguchi, Synlett, 849 (2008).
6. Tomoda et al. have shown that the treatment of alkyne with phenylselenocyanate and copper
(II) halides in the presence of triethylamine gave the corresponding (E)-β-halo alkenyl phenyl
selenides. In this method, they have described that halogen atom came from the copper(II) halide
[2f].
7. It was reported that the treatment of alkynes bearing electron-withdrawing groups with phenylse-
lenyl halides (PhSeX: X = Cl and Br) gave β-halo alkenyl phenyl selenides, in which the
phenylseleno group was introduced on the α-carbon of the starting materials [2b].