Copper(I) iodide catalyzed cross-coupling reaction of terminal alkynes with 1-bromoalkynes: A simple synthesis of unsymmetrical buta-1,3-diynes

Article abstract of DOI:10.1055/s-0030-1259998

A simple synthesis of unsymmetrical buta-1,3-diynes by cross-coupling of terminal alkynes with 1-bromoalkynes in the presence of copper(I) iodide and tris(o-tolyl)phosphine was developed that gives good yields under simple and mild reaction conditions. The scope and limitations of the cross-coupling reaction were investigated. Georg Thieme Verlag Stuttgart · New York.

Full text of DOI:10.1055/s-0030-1259998

PAPER
1541
Copper(I) Iodide Catalyzed Cross-Coupling Reaction of Terminal Alkynes
with 1-Bromoalkynes: A Simple Synthesis of Unsymmetrical Buta-1,3-diynes
Catalytic
Cros
h
s-Coupling o
i
f
T
erm
h
inal
A
lkynes
u
w
ith 1-Brom
a
oalkyne
s
Wang,a Lin Yu,a Pinhua Li,a Lingguo Meng,a Lei Wang*a,b
a
Department of Chemistry, Huaibei Normal University, Huaibei, Anhui 235000, P. R. of China
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
Shanghai 200032, P. R. of China
b
Fax +86(561)3090518; E-mail: leiwang@chnu.edu.cn
Received 27 January 2011; revised 6 March 2011
iodide with tris(o-tolyl)phosphine as a ligand under mild
and simple reaction conditions.
Abstract: A simple synthesis of unsymmetrical buta-1,3-diynes by
cross-coupling of terminal alkynes with 1-bromoalkynes in the
presence of copper(I) iodide and tris(o-tolyl)phosphine was devel-
oped that gives good yields under simple and mild reaction condi-
tions. The scope and limitations of the cross-coupling reaction were
investigated.
Initially, our investigation was directed towards optimiz-
ing the reaction conditions for the cross-coupling of 1-
ethynyl-4-methoxybenzene (1a) with (bromoethy-
nyl)benzene (2a) in the presence of copper(I) iodide as a
catalyst. First, we examined the effect of the ligand on the
cross-coupling reaction, and our results are shown in
Table 1. Only a trace of the cross-coupling product 3a was
detected by TLC in the absence of a ligand (Table 1, entry
1). However, the cross-coupling product 3a was obtained
in 94% yield when tris(o-tolyl)phosphine was used as the
ligand in ethanol (entry 2). The use of triphenylphosphine
as the ligand also gave 3a in a comparable yield (entry 3).
Other phosphine ligands, such as diphenyl(p-tolyl)phos-
phine, tri-tert-butylphosphine, or ethane-1,2-diyl-
bis(diphenylphosphine) (DPPE) gave inferior results
(entries 4–6). Poor yields were also obtained with pyri-
dine, 1,4-diazabicyclo[2,2,2]octane (DABCO), 1,10-
phenanthroline, quinoline, or 2-acetylcyclohexanone (en-
tries 7–11, respectively).When 2-aminoethanol was used
as the ligand, no cross-coupling product was detected (en-
try 12). Further investigations in various solvents showed
that ethanol is the optimal solvent for the cross-coupling
reaction (entry 2). Slightly lower yields of product 3a
were obtained when acetonitrile, 1,2-dichloroethane
(DCE), nitromethane, N,N-dimethylformamide (DMF),
or toluene was used as the solvent instead of ethanol,
whereas only moderate yields were obtained in 1,4-diox-
ane, tetrahydrofuran (THF), or water (entries 13–20).
Key words: alkynes, catalysis, cross-coupling, alkadiynes
Buta-1,3-diynes are important building blocks in the
organic syntheses of natural products,1 industrial and
pharmaceutical
intermediates,2
organic–inorganic
composites,3 and electronic and optical materials.4 Nu-
merous methods have been developed for the preparation
of buta-1,3-diynes. An efficient and useful method for
preparing symmetrical buta-1,3-diynes by treatment of
terminal alkynes with copper(I) chloride in the presence
of ammonium hydroxide was developed by Glaser in
1869.5 Subsequently, many improved methods for prepar-
ing buta-1,3-diynes have been developed on the basis of
Glaser’s discovery.6 Palladium(0)/copper(I)-catalyzed
coupling is also an important method for the synthesis of
buta-1,3-diynes.7 However, most of these coupling reac-
tions are homo-coupling reactions of terminal acetylenes
to form symmetrical buta-1,3-diynes.8 Therefore, the syn-
thesis of unsymmetrical buta-1,3-diynes has attracted a
great deal of attention over a long period.9 Currently, the
main methods used for constructing unsymmetrical buta-
1,3-diynes are the Cadiot–Chodkiewicz coupling reaction
and its modifications.10 Though powerful in many cases,
these coupling reactions frequently give large amounts of
the symmetrical buta-1,3-diyne products. Recently, Lei
described an efficient method for the synthesis of unsym-
metrical buta-1,3-diynes from terminal alkynes and 1-bro-
moalkynes in the presence of a palladium catalyst;11
however, such catalysts are expensive and unstable to air.
To improve this cross-coupling reaction, we investigated
the possibility of performing the cross-coupling of termi-
nal alkynes with 1-bromoalkynes in the absence of a pal-
ladium catalyst. Here, we report a new route to
unsymmetrical buta-1,3-diynes from terminal alkynes and
1-bromoalkynes by coupling in the presence of copper(I)
Next, we examined the influence of the copper salt and the
base on the cross-coupling reaction, and our results are
summarized in Table 2. Various copper salts were
screened as catalysts in the presence of tris(o-tolyl)phos-
phine in ethanol, and copper(I) iodide was found to be the
optimal choice (Table 2, entry 1). The yield of the product
3a decreased when copper(I) bromide or chloride was
used instead of the iodide (entries 2 and 3). Other copper
salts, such as copper(II) chloride, copper(II) bromide,
bis(acetylacetonato)copper(II), or copper(II) triflate gave
inferior results, generating 3a in 84, 82, 56 and 77% yield,
respectively (entries 4–7). With regard to the effect of
bases on the reaction, potassium carbonate was found to
be an excellent base, and trisodium phosphate was also ef-
fective (entries 1 and 8, respectively)). Use of cesium car-
bonate, sodium hydroxide, or potassium tert-butoxide
SYNTHESIS 2011, No. 10, pp 1541–1546
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x.
x
x
.
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0
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Advanced online publication: 11.04.2011
DOI: 10.1055/s-0030-1259998; Art ID: H15711SS
© Georg Thieme Verlag Stuttgart · New York

1542
S. Wang et al.
PAPER
Table 1 Effect of the Ligand and Solvent on the Cross-Coupling Reaction
CuI (10 mol%)
ligand (20 mol%)
Br
+
MeO
MeO
K2CO3, solvent
1a
2a
3a
Entrya
1
Ligand
–
Solvent
Yieldb (%)
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
MeCN
DCE
<10
94
91
59
71
63
34
42
45
44
42
2
P(o-Tol)3
PPh3
3
4
(p-Tol)PPh2
P(t-Bu)3
DPPE
5
6
7
pyridine
DABCO
8
9
1,10-phenanthroline
quinoline
10
11
12
13
14
15
16
17
18
19
20
2-acetylcyclohexanone
HO(CH2)2NH2
P(o-Tol)3
c
–
82
84
78
79
74
67
61
57
P(o-Tol)3
P(o-Tol)3
MeNO2
DMF
P(o-Tol)3
P(o-Tol)3
toluene
1,4-dioxane
THF
P(o-Tol)3
P(o-Tol)3
P(o-Tol)3
H2O
a Reaction conditions: 1a (0.5 mmol), 2a (0.65 mmol), CuI (0.05 mmol), ligand (0.10 mmol), K2CO3 (1.0 mmol), solvent (2.0 mL), 100 °C, 12
h, under N2.
b Isolated yield.
c Not detected.
gave moderate yields of 3a (entries 9–11). The organic To evaluate the scope of the cross-coupling reaction in
bases triethylamine and 1,8-diazabicyclo[5.4.0]undec-7- more detail, several terminal alkynes were also tested in
ene (DBU) gave the cross-coupling product in 71 and the optimized reaction conditions. Clearly, substituents on
59%, respectively (entries 12 and 13).
the aromatic terminal alkynes had no obvious effect on the
yield of the reaction (entries 4–9). A good yield of the
product was obtained when 1-ethynyl-2-nitrobenzene
(1h) was used as reaction substrate (entry 10). The het-
eroaromatic terminal alkyne 3-ethynylpyridine (1i) gave
the corresponding product 3i in 77% yield (entry 11). Al-
iphatic alkynes also gave the desired cross-coupling prod-
ucts in good yields (entries 12–16 and 18). Note that the
reaction of 5-chloropent-1-yne (1m) with 2a gave the de-
sired product 3n in 81% yield, and the chloro group was
well tolerated (entry 17). Also note that the cross-coupling
reactions of terminal aromatic alkynes with 2-arylethynyl
bromides were clean and gave excellent yields of the
With these optimized reaction conditions in hand, we ex-
plored the scope and efficiency of the cross-coupling re-
action, as shown in Table 3. Various terminal alkynes and
1-bromoalkynes were used as the reaction substrates, and
the corresponding unsymmetrical buta-1,3-diynes were
generally obtained in good yields. Various polar alkynes
were used to overcome problems in separation. Aromatic
1-bromoalkynes 2, containing various substituents, react-
ed with terminal alkynes 1 to give the corresponding prod-
ucts 3 in good yields (Table 3, entries 2 and 4). Aliphatic
1-bromoalkynes, such as 1-bromooct-1-yne (2c), also
gave the desired product in 78% yield (entry 3).
Synthesis 2011, No. 10, 1541–1546 © Thieme Stuttgart · New York

PAPER
Catalytic Cross-Coupling of Terminal Alkynes with 1-Bromoalkynes
1543
Table 2 Effect of the Copper Source and Base on the Cross-Coupling Reaction
Cu salt
P(o-Tol)3
MeO
MeO
+
Br
EtOH, base
1a
2a
3a
Entrya
Cu salt
CuI
Base
Yieldb (%)
1
2
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Na3PO4
Cs2CO3
NaOH
t-BuOK
Et3N
94
80
79
84
82
56
77
91
69
64
67
71
59
CuCl
CuBr
CuCl2
CuBr2
Cu(acac)2
Cu(OTf)2
CuI
3
4
5
6
7
8
9
CuI
10
11
12
13
CuI
CuI
CuI
CuI
DBU
a Reaction conditions: 1a (0.5 mmol), 2a (0.65 mmol), copper salt (0.05 mmol), P(o-Tol)3 (0.10 mmol), base (1.0 mmol), EtOH (2.0 mL),
100 °C, 12 h, under N2.
b Isolated yield.
cross-coupling products. The cross-coupling reactions of tions of terminal aliphatic alkynes with 2-alkylethynyl
terminal aromatic or aliphatic alkynes with 2-arylethynyl bromides resulted in no cross-coupling product, and about
bromides gave the corresponding cross-coupling products a 10% yield of the homocoupling product was detected to-
in 73–90% yields, along with less than 10% of the corre- gether with unchanged starting materials, which could be
sponding homo-coupled byproducts. However, the reac- recovered.
Table 3 Copper(I) Iodide Catalyzed Cross-Coupling Reaction of Terminal Alkynes with 1-Bromoalkynes
CuI (10 mol%)
P(o-Tol)3 (20 mol%)
R1
+
R1
R2
Br
R2
K2CO3, EtOH
1
2
3
Entrya
1
1
2
3
Yieldb (%)
94
MeO
1a
Br
MeO
3a
2a
2b
Br
MeO
3b
2
3
4
1a
90
78
90
MeO
3c
1a
1b
Br
2c
MeO
2d
Br
3b
Synthesis 2011, No. 10, 1541–1546 © Thieme Stuttgart · New York

1544
S. Wang et al.
PAPER
Table 3 Copper(I) Iodide Catalyzed Cross-Coupling Reaction of Terminal Alkynes with 1-Bromoalkynes (continued)
CuI (10 mol%)
P(o-Tol)3 (20 mol%)
R1
+
R1
R2
Br
R2
K2CO3, EtOH
1
2
3
Entrya
5
1
2
3
Yieldb (%)
89
MeO
MeO
2a
1c
3d
3e
OMe
6
7
8
9
2d
2a
2d
2d
92
96
94
88
1d
1e
3f
3a
1f
Cl
Cl
OMe
3g
1g
NO2
NO2
10
2a
81
1h
3h
11
12
2a
2a
77
80
N
N
1i
3i
1j
3j
13
14
15
2a
2d
2a
86
73
90
1k
1k
3k
3c
1l
1l
3l
MeO
3m
16
17
2d
2a
79
81
Cl
Cl
1m
3n
O
18
2a
92
O
1n
3o
a Reaction conditions: Terminal alkyne (0.50 mmol), 1-bromoalkyne (0.65 mmol), CuI (0.05 mmol), P(o-Tol)3 (0.10 mmol), K2CO3 (1.0 mmol),
EtOH (2.0 mL), 100 °C, 12 h, under N2.
b Isolated yields.
Synthesis 2011, No. 10, 1541–1546 © Thieme Stuttgart · New York

PAPER
Catalytic Cross-Coupling of Terminal Alkynes with 1-Bromoalkynes
1545
1-tert-Butyl-4-[4-(4-methoxyphenyl)buta-1,3-diyn-1-yl]ben-
In summary, we have developed a new route to unsym-
metrical buta-1,3-diynes from terminal alkynes and 1-bro-
moalkynes by cross-coupling in the presence of copper(I)
iodide and tris(o-tolyl)phosphine as ligand in ethanol un-
der mild conditions. This method provides an efficient
and simple technique for the synthesis of unsymmetrical
buta-1,3-diynes that compares favorably with previous
methods for the syntheses of these compounds. Applica-
tions and the development of our new reaction system are
now under investigation.
zene (3e)
1H NMR (CDCl3, 400 MHz): d = 7.50–7.48 (m, 4 H), 7.38 (d,
J = 8.4 Hz, 2 H), 6.88 (d, J = 8.8 Hz, 2 H), 3.84 (s, 3 H), 1.34 (s, 9
H).
13C NMR (CDCl3, 100 MHz): d = 160.22, 152.43, 134.04, 132.17,
125.43, 118.83, 114.09, 113.74, 81.39, 81.28, 73.48, 72.88, 55.27,
34.84, 31.05.
HRMS (ESI): m/z [M]+ calcd for C21H20O: 288.1514; found:
288.1518.
4-(4-Phenylbuta-1,3-diyn-1-yl)biphenyl (3f)
1H NMR (CDCl3, 400 MHz): d = 7.60–7.52 (m, 8 H), 7.46–7.42 (m,
2 H), 7.38–7.31 (m, 4 H).
13C NMR (CDCl3, 100 MHz): d = 141.90, 140.03, 132.92, 132.48,
129.19, 128.88, 128.43, 127.83, 127.08, 127.01, 121.75, 120.55,
81.84, 81.50, 74.55, 73.98.
1
All H NMR and 13C NMR spectra were recorded on a Bruker
DMX-400 MHz FT-NMR spectroscope. Chemical shifts are given
as d value with reference to TMS as internal standard. High-resolu-
tion mass spectra were recorded on a Waters Micromass GCT in-
strument. Products were purified by flash column chromatography
on 230–400 mesh silica gel.
HRMS (ESI): m/z [M]+ calcd for C22H14: 278.1096; found:
278.1093.
1-Methoxy-4-(4-phenylbuta-1,3-diyn-1-yl)benzene (3a);10b
Typical Procedure
1-Chloro-4-[4-(4-methoxyphenyl)buta-1,3-diyn-1-yl]benzene
(3g)10b
A reaction flask was charged with CuI (9.6 mg, 0.05 mmol), P(o-
Tol)3 (30.4 mg, 0.10 mmol), K2CO3 (138 mg, 1.0 mmol), 1-ethynyl-
4-methoxybenzene (1a; 76 mg, 0.50 mmol), 1-(2-bromoethy-
nyl)benzene (2a; 118 mg, 0.65 mmol), and anhyd EtOH (2.0 mL).
The mixture was stirred for 12 h at 100 °C then cooled to r.t. The
mixture was diluted with EtOAc (3 × 5.0 mL), filtered through a
pad of Celite, and concentrated in vacuo. The residue was purified
by flash column chromatography (silica gel, PE or cyclohexane gra-
dient); yield: 109 mg (94%).
1H NMR (CDCl3, 400 MHz): d = 7.53 (dd, J = 1.6, 7.6 Hz, 2 H),
7.48 (d, J = 8.8 Hz, 2 H), 7.37–7.31 (m, 3 H), 6.87 (d, J = 8.8 Hz, 2
H), 3.82 (s, 3 H).
13C NMR (CDCl3, 100 MHz): d = 160.31, 134.08, 132.38, 129.00,
128.38, 121.93, 114.11, 113.61, 81.78, 80.98, 74.13, 72.69, 55.29.
1H NMR (CDCl3, 400 MHz): d = 7.50–7.44 (m, 4 H), 7.32 (d,
J = 8.4 Hz, 2 H), 6.87 (d, J = 8.8 Hz, 2 H), 3.84 (s, 3 H).
13C NMR (CDCl3, 100 MHz): d = 160.42, 135.12, 134.15, 133.58,
128.80, 120.47, 114.15, 113.42, 82.37, 79.75, 75.11, 72.47, 55.34.
1-Nitro-2-(4-phenylbuta-1,3-diyn-1-yl)benzene (3h)
1H NMR (CDCl3, 400 MHz): d = 8.12 (d, J = 8.0 Hz, 1 H), 7.73 (d,
J = 8.0 Hz, 1 H), 7.63–7.60 (m, 1 H), 7.57–7.54 (m, 2 H), 7.53–7.49
(m, 1 H), 7.43–7.34 (m, 3 H).
13C NMR (CDCl3, 100 MHz): d = 135.80, 133.02, 132.62, 129.67,
129.33, 128.48, 124.93, 121.18, 117.70, 84.79, 81.47, 76.09, 73.60.
HRMS (ESI): m/z [M]+ calcd for C16H9NO2: 247.0633; found:
247.0636.
1-Methoxy-4-[4-(4-methylphenyl)buta-1,3-diyn-1-yl]benzene
(3b)12
3-(4-Phenylbuta-1,3-diyn-1-yl)pyridine (3i)13
1H NMR (CDCl3, 400 MHz): d = 8.77 (s, 1 H), 8.59 (d, J = 2.8 Hz,
1 H), 7.81 (d, J = 7.6 Hz, 1 H), 7.55 (d, J = 6.8 Hz, 2 H), 7.42–7.34
(m, 3 H), 7.30–7.28 (m, 1 H).
1H NMR (CDCl3, 400 MHz): d = 7.48 (d, J = 8.8 Hz, 2 H), 7.43 (d,
J = 8.0 Hz, 2 H), 7.15 (d, J = 8.0 Hz, 2 H), 6.87 (d, J = 8.8 Hz, 2 H),
3.84 (s, 3 H), 2.38 (s, 3 H).
13C NMR (CDCl3, 100 MHz): d = 153.02, 149.14, 139.24, 132.52,
13C NMR (CDCl3, 100 MHz): d = 160.23, 139.38, 134.05, 132.31,
129.18, 118.80, 114.09, 113.75, 81.43, 81.28, 73.49, 72.81, 55.30,
21.60.
129.50, 128.45, 123.00, 121.24, 119.19, 82.71, 77.90, 77.15, 73.31.
Nona-1,3-diyn-1-ylbenzene (3j)11
1H NMR (CDCl3, 400 MHz): d = 7.48 (dd, J = 1.6, 7.6 Hz, 2 H),
7.34–7.28 (m, 3 H), 2.36 (t, J = 7.2 Hz, 2 H), 1.62–1.55 (m, 2 H),
1.45–1.32 (m, 4 H), 0.92 (t, J = 6.8 Hz, 3 H).
1-Deca-1,3-diyn-1-yl-4-methoxybenzene (3c)15
1H NMR (CDCl3, 400 MHz): d = 7.41 (d, J = 8.8 Hz, 2 H), 6.82 (d,
J = 8.8 Hz, 2 H), 3.80 (s, 3 H), 2.35 (t, J = 7.2 Hz, 2 H), 1.60–1.53
(m, 2 H), 1.46–1.38 (m, 2 H), 1.36–1.27 (m, 4 H), 0.90 (t, J = 6.8
Hz, 3 H).
13C NMR (CDCl3, 100 MHz): d = 132.45, 128.75, 128.29, 122.08,
84.87, 74.64, 74.36, 65.00, 30.99, 27.92, 22.15, 19.52, 13.91.
13C NMR (CDCl3, 100 MHz): d = 159.96, 133.99, 114.00, 113.98,
84.17, 74.77, 73.10, 65.14, 55.23, 31.28, 28.53, 28.25, 22.50, 19.55,
14.02.
Deca-1,3-diyn-1-ylbenzene (3k)
1H NMR (CDCl3, 400 MHz): d = 7.48 (d, J = 7.2 Hz, 2 H), 7.36–
7.26 (m, 3 H), 2.37 (t, J = 7.2 Hz, 2 H), 1.62–1.55 (m, 2 H), 1.47–
1.40 (m, 2 H), 1.36–1.31 (m, 4 H), 0.92 (t, J = 6.8 Hz, 3 H).
1-Methoxy-3-(4-phenylbuta-1,3-diyn-1-yl)benzene (3d)
1H NMR (CDCl3, 400 MHz): d = 7.55 (d, J = 7.2 Hz, 2 H), 7.40–
7.34 (m, 3 H), 7.29–7.25 (m, 1 H), 7.15 (d, J = 7.6 Hz, 1 H), 7.07 (s,
1 H), 6.96–6.94 (m, 1 H), 3.82 (s, 3 H).
13C NMR (CDCl3, 100 MHz): d = 159.22, 132.47, 129.52, 129.22,
128.42, 125.03, 122.65, 121.67, 116.98, 115.99, 81.55, 81.43,
73.80, 73.65, 55.27.
13C NMR (CDCl3, 100 MHz): d = 132.44, 128.74, 128.29, 122.08,
84.85, 74.63, 74.38, 65.00, 31.27, 28.53, 28.20, 22.50, 19.55, 14.03.
HRMS (ESI): m/z [M]+ calcd for C16H18: 210.1409; found:
210.1411.
1-Dodeca-1,3-diyn-1-ylbenzene (3l)14
1H NMR (CDCl3, 400 MHz): d = 7.49 (dd, J = 1.2, 7.2 Hz, 2 H),
7.35–7.29 (m, 3 H), 2.37 (t, J = 7.2 Hz, 2 H), 1.60–1.55 (m, 2 H),
1.45–1.42 (m, 2 H), 1.36–1.31 (m, 8 H), 0.92 (t, J = 7.2 Hz, 3 H).
HRMS (ESI): m/z [M]+ calcd for C17H12O: 232.0888; found:
232.0892.
Synthesis 2011, No. 10, 1541–1546 © Thieme Stuttgart · New York

1546
S. Wang et al.
PAPER
13C NMR (CDCl3, 100 MHz): d = 132.41, 128.71, 128.26, 122.07,
84.80, 74.60, 74.40, 65.03, 31.80, 29.13, 29.04, 28.85, 28.23, 22.63,
19.53, 14.06.
913. (b) Aida, T.; Tajima, K. Angew. Chem. Int. Ed. 2001,
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1-Dodeca-1,3-diyn-1-yl-4-methoxybenzene (3m)16
1H NMR (CDCl3, 400 MHz): d = 7.42 (d, J = 8.8 Hz, 2 H), 6.83 (d,
J = 8.8 Hz, 2 H), 3.82 (s, 3 H), 2.36 (t, J = 7.2 Hz, 2 H), 1.61–1.54
(m, 2 H), 1.44–1.42 (m, 2 H), 1.34–1.28 (m, 8 H), 0.90 (t, J = 6.8
Hz, 3 H).
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13C NMR (CDCl3, 100 MHz): d = 159.91, 133.97, 113.94, 113.83,
84.18, 74.74, 73.05, 65.09, 55.22, 31.79, 29.13, 29.04, 28.84, 28.26,
22.63, 19.53, 14.09.
(7-Chlorohepta-1,3-diyn-1-yl)benzene (3n)
1H NMR (CDCl3, 400 MHz): d = 7.49 (d, J = 6.4 Hz, 2 H), 7.38–
7.29 (m, 3 H), 3.69 (t, J = 6.4 Hz, 2 H), 2.58 (t, J = 6.8 Hz, 2 H),
2.07–2.00 (m, 2 H).
13C NMR (CDCl3, 100 MHz): d = 132.46, 128.94, 128.32, 121.72,
82.41, 75.14, 73.99, 66.00, 43.40, 30.88, 16.97.
HRMS (ESI): m/z [M]+ calcd for C13H11Cl: 202.0549; found:
202.0548.
[5-(Benzyloxy)penta-1,3-diyn-1-yl]benzene (3o)9
1H NMR (CDCl3, 400 MHz): d = 7.54 (dd, J = 1.2, 8.0 Hz, 2 H),
7.42–7.33 (m, 8 H), 4.67 (s, 2 H), 4.35 (s, 2 H).
13C NMR (CDCl3, 100 MHz): d = 137.04, 132.55, 129.28, 128.43,
128.37, 128.10, 127.94, 121.32, 78.68, 78.05, 73.32, 71.67, 71.10,
57.68.
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synthesis.
Acknowledgment
We gratefully acknowledge the financial support provided by the
National Natural Science Foundation of China (No. 20972057,
21002039).
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2004, 6, 3601. (b) Nishihara, Y.; Ikegashira, K.; Mori, A.;
Hiyama, T. Tetrahedron Lett. 1988, 39, 4075.
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Synthesis 2011, No. 10, 1541–1546 © Thieme Stuttgart · New York