Palladium-catalyzed cross-coupling reactions of triarylbismuthanes with terminal alkynes under aerobic conditions

Article abstract of DOI:10.1016/j.jorganchem.2015.06.029

Abstract A simple Pd-catalyzed Sonogashira-type cross-coupling reaction using of triarylbismuthanes is described. The reaction of triarylbismuthanes with terminal alkynes in the presence of 5 mol% of Pd(OAc)₂, 6 equiv. AgF and 6 equiv. K₃PO₄ at room temperature afforded the coupling products in good to excellent yield. The reaction proceeded effectively under aerobic conditions, and all three aryl groups on bismuth could be transferred to the coupling products. The reaction was sensitive to the electronic nature of the triarylbismuthanes: substrates bearing an electron-withdrawing group on the aromatic ring showed higher reactivity than those having an electron-donating group.

Full text of DOI:10.1016/j.jorganchem.2015.06.029

Journal of Organometallic Chemistry 794 (2015) 70e75
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Palladium-catalyzed cross-coupling reactions of triarylbismuthanes
with terminal alkynes under aerobic conditions
Mio Matsumura a, Mizuki Yamada a, Toshiyuki Tsuji b, Yuki Murata b, Naoki Kakusawa b,
,
*
Shuji Yasuike a
a School of Pharmaceutical Sciences, Aichi Gakuin University, 1-100 Kusumoto-cho, Chikusa-ku, Nagoya 464-8650, Japan
b Faculty of Pharmaceutical Sciences, Hokuriku University, Ho-3 Kanagawa-machi, Kanazawa 920-1181, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
A
simple Pd-catalyzed Sonogashira-type cross-coupling reaction using of triarylbismuthanes is
Received 13 April 2015
Received in revised form
15 June 2015
Accepted 18 June 2015
Available online 29 June 2015
described. The reaction of triarylbismuthanes with terminal alkynes in the presence of 5 mol% of
Pd(OAc)2, 6 equiv. AgF and 6 equiv. K3PO4 at room temperature afforded the coupling products in good to
excellent yield. The reaction proceeded effectively under aerobic conditions, and all three aryl groups on
bismuth could be transferred to the coupling products. The reaction was sensitive to the electronic nature
of the triarylbismuthanes: substrates bearing an electron-withdrawing group on the aromatic ring
showed higher reactivity than those having an electron-donating group.
Keywords:
© 2015 Elsevier B.V. All rights reserved.
Palladium-catalyzed cross-coupling reaction
Triarylbismuthane
Terminal alkyne
Aerobic condition
Sonogashira-type reaction
1. Introduction
developed from research of catalyst and ligand by several groups
[9e12]. Recently, Zhu et al. carried out the reaction of terminal al-
The copper(Cu)-palladium(Pd)-catalyzed coupling reaction of
terminal alkynes with aryl or vinyl halides to give enynes is known
as the Sonogashira reaction, and it has become an extremely
powerful tool for constructing conjugated acetylenes [1e4]. The
Sonogashira reaction conventionally employs a Pd-phosphine
complex as the catalyst, along with a Cu salt as the co-catalyst
and excess amine as the solvent and base [1e5]. However, the Cu
co-catalyst sometime lead to the Glaser-type homo-coupling of
terminal alkynes to form 1,3-diynes under aerobic conditions [6,7].
Moreover, amines have a characteristic foul smell and pungent
flavor. In the past decades, various modifications of the Sonogashira
reaction have been developed. For example, the use of different aryl
substances as the pseudo-halide component and silver reagents as
additives has been investigated for C(Ar)‒C(sp) bond formation. In
2003, Zou et al. reported a procedure for constructing internal al-
kynes through the cross-coupling reaction of terminal alkynes and
arylboronic acids catalyzed by a Pd(dppf)Cl2eAgO system [8]. Since
then, this type of reaction using arylboronic acids has been
kynes with hypervalent aryl iodonium salts using a PdCl2eAgI
system [13]. Furthermore, Cheng et al. reported that aryl trime-
thoxysilanes are useful arylating agents when using a Pd(dppf)
Cl2eAgF system [14].
Organobismuth compounds are typically non-toxic, environ-
mentally benign, and potentially useful candidates as synthetic
reagents [15e17]. The utility of trivalent organobismuth com-
pounds such as triarylbismuthanes [Ar3Bi] has attracted much
attention in recent years, particularly through their use in the Pd-
catalyzed C(Ar)‒C(Ar, sp2) bond formation reaction with aryl or
vinyl halides [18e22]. Two methods are known for the synthesis of
internal alkynes using the Pd-catalyzed coupling reaction of orga-
nobismuth compounds. Shimada et al. reported the reaction of aryl
halides with Bi-phenylethynyl-tetrahydrodibenz[c,f] [1,5] aza-
bismocines catalyzed by a Pd(OAc)2/dppf system and CsF under an
inert atmosphere [23]. Rao et al. have developed the domino re-
action of 1,1-dibromo-1-alkenes with triarylbismuthanes in the
presence of Pd(PPh3)4 catalyst with a base under an inert atmo-
sphere [24]. However, to be best of our knowledge, Pd-catalyzed
C(Ar)-C(sp) bond formation by the reaction of terminal alkynes
with triarylbismuthanes under aerobic conditions has not hitherto
been reported. Herein, we report a novel Sonogashira-type reaction
* Corresponding author.
E-mail address: s-yasuik@dpc.agu.ac.jp (S. Yasuike).
http://dx.doi.org/10.1016/j.jorganchem.2015.06.029
0022-328X/© 2015 Elsevier B.V. All rights reserved.

M. Matsumura et al. / Journal of Organometallic Chemistry 794 (2015) 70e75
71
using triarylbismuthanes as pseudo-halides in the presence of a
silver salt and base under aerobic conditions.
aerobic conditions (entries 1e4). The expected cross-coupling
compound 10 was obtained in high yields when 1a was
employed as a substrate (entry 1). Moreover, all three phenyl
groups on bismuth in 1a participated in this reaction. It is known
that 2 and 4 are effective reagents as pseudo-halide compounds in
C(Ar)‒C(Ar, sp2) bond formation, for example, in Heck- [25] and
Stille-type [26] cross-coupling reactions. In this reaction however,
pentavalent organobismuth compounds 2, 3, and 4 were found to
be less reactive (entries 2e4). We also evaluated the reaction using
organoantimony compounds, such as 5, 6, 7, and 8 (entries 5e8).
However, all these compounds gave the product 10 in poor yield.
These results show that the reactivity of the metal reagents is
considerably affected by the valence [(III), (V)] and the kind (Bi, Sb)
of the constitutive metal. Several available palladium catalysts were
then screened in the reaction between 1a and 9a (entries 1, 9e11).
2. Results and discussion
We initially focused on the determination of the best experi-
mental conditions for the cross-coupling of phenyl acetylene (9a)
with organobismuth and organoantimony compounds (1e8), such
as Ph3Bi (1a), Ph3BiCl2 (2), Ph3BiF2 (3), Ph3Bi(OAc)2 (4), Ph3Sb (5),
Ph3SbCl2 (6), Ph3SbF2 (7) and Ph3Sb(OAc)2 (8). The results including
screening of suitable catalysts, bases, additives, and active aryl
substances are summarized in Table 1. We fiest performed the re-
action of 9a (3 equiv.) with organobismuth such as 1a, 2, 3, and 4 to
compare their reactivity, using 5 mol% of Pd(OAc)2, AgF (6 equiv.)
and K3PO4 (6 equiv.) in acetonitrile at room temperature under
Table 1
Pd-catalyzed cross-coupling reaction of organobismuth and antimony compounds 1e8 with phenylacetylene 9a.a
Entry
Substrate
Pd cat.
Base (equiv)
Additive (equiv)
Time (h)
Yield (%)
10b
11b
1
2
3
4
5
6
7
8
1a
2
3
4
5
6
7
8
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
PdCl2
PdCl2(PPh3)2
PdCl2(dppf)
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
K3PO4 (6)
K3PO4 (6)
K3PO4 (6)
K3PO4 (6)
K3PO4 (6)
K3PO4 (6)
K3PO4 (6)
K3PO4 (6)
K3PO4 (6)
K3PO4 (6)
K3PO4 (6)
NaHCO3 (6)
AcOK (6)
K2CO3 (6)
Na2CO3 (6)
tBuOK (6)
K3PO4 (6)
K3PO4 (6)
K3PO4 (6)
K3PO4 (6)
K3PO4 (6)
K3PO4 (3)
e
AgF (6)
AgF (6)
AgF (6)
AgF (6)
AgF (6)
AgF (6)
AgF (6)
AgF (6)
AgF (6)
AgF (6)
AgF (6)
AgF (6)
AgF (6)
AgF (6)
AgF (6)
AgF (6)
AgOAc (6)
AgNO3 (6)
Ag2O (6)
CsF (6)
TBAF$H2O (6)
AgF (6)
AgF (6)
AgF (3)
e
2
24
24
24
24
24
24
24
24
2
99 (96)c
29
2
1
5
<1
2
7
94
72
67
57
53
52
43
<1
34
6
<1
<1
ND
<1
ND
ND
<1
<1
<1
1
<1
<1
ND
<1
<1
<1
<1
<1
1
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26d
27e
2
4
4
24
24
24
24
24
24
24
24
24
24
24
24
24
2
4
<1
<1
65
60
31
<1
29
82
<1
<1
<1
6
2
4
K3PO4 (6)
K3PO4 (6)
K3PO4 (6)
K3PO4 (6)
AgF (6)
AgF (6)
<1
2
a
Condition: 1e6 (0.5 mmmol), 7a (1.5 mmol), Pd cat (0.025 mmol), base (3 mmol), additive (3 mmol).
GC yield using dibenzyl as internal standard. The yield 100% corresponds to the formation of 1.5 mmol of 10 and 0.75 mmol of 11.
Isolated yield.
Pd. cat (1 mol%).
Under Ar.
b
c
d
e

72
M. Matsumura et al. / Journal of Organometallic Chemistry 794 (2015) 70e75
Of these, Pd(OAc)2 appeared to be the optimal catalyst for the re-
action in terms of the yield of the coupling product 10 (99%) and the
reaction time (2 h). Alternative bases systems such as NaHCO3,
AcOK, K2CO3, Na2CO3, and t-BuOK were also examined (entries 1,
13e16). The results showed that K3PO4 was the most effective. Of
the additives screened, such as silver salts and fluoride reagents,
only AgF showed high reactivity (entries 1, 17e21). The loading of
AgF and K3PO4 was also investigated (entries 22e25): however, the
initial conditions, employing 6 equiv. AgF and 6 equiv. K3PO4 gave
the best result. Unexpectedly, the reaction proceeded even in the
absence of K3PO4 when using 6 equiv. AgF to give 10 in moderate
yield (entry 23). It is apparent that the reaction is sensitive to
catalyst loading, as decreasing the loading of Pd(OAc)2 from 5 mol%
to 1 mol% gave a significantly reduced yield of 10 (29%, entry 26).
When the reaction was performed under an argon atmosphere, the
coupling product was obtained in a slightly lower yield (entry 27).
Screening of solvents showed that the reaction proceed effectively
in DMF (92%) and CH2Cl2 (79%) at 24 h, whereas MeOH (27%), THF
(2%), and toluene (<1%) gave inferior results. The reaction under
aerobic conditions is simple and easy to operate. Thus, the best
reaction conditions were determined to be as follows: treatment of
triphenylbismuthane (1a) with phenyl acetylene (9a) using of
5 mol% Pd(OAc)2 as the catalyst, 6 equiv. AgF and 6 equiv. K3PO4 in
acetonitrile at room temperature under aerobic conditions.
In order to understand the scope and limitations of the above
mentioned protocol, the reactions of various triarylbismuthanes
(1aei) and terminal alkynes (9aek) were examined under the
optimized reaction conditions. The results are summarized in
Table 2. The yields of the coupling products are based on all three
aryl groups on the bismuth compounds taking part in the reaction.
Initially, triphenylbismuthanes (1a) were reacted with a variety of
terminal alkynes (9bek: 3 equiv.) (entries 1e10). Terminal alkynes
with aryl 9bee, heteroaryl 9f, vinyl 9g, and alkyl 9h groups afforded
the corresponding coupling products 12e18 in yields of 65e90%.
The nature of the aryl substituent on the alkynes (9bee) has a
distinctive effect on the rate of the coupling reaction. The reaction
time in the case of alkynes with electron-donating groups on the
aromatic ring is shorter than that for electron-withdrawing groups.
The traditional Sonogashira reaction leads to low yields for
electron-deficient alkynes. Notably, the electron-deficient ethyl
propiolate (9i) also gave moderate yields (entry 8). Unfortunately,
the reaction of 1a with ethynyltriphenylsilane (9j) and 1,1-
dimethylpropargyl alcohol (9k) gave a complex mixture under
these conditions (entries 9, 10). It was assumed that reagents (9j, k)
and products (20, 21) was injured by excess amount of AgF and/or
K3PO4. Various substituted triarylbismuthanes (1bei) were reacted
with phenyl acetylene (9a) under the same reaction conditions.
Bismuthanes 1bei with both electron-donating and electron-
withdrawing groups on the aromatic ring afforded the corre-
sponding cross-coupling products in excellent to moderate yields,
expect for 1i (entries 11e18). This result is in contrast to the pre-
vious shown results (entries 11e15), where the Sonogashira-type
reaction of triarylbismuthanes bearing electron-withdrawing aryl
groups proceeded more rapidly than those of triarylbismuthanes
bearing electron-donating aryl groups. In the methyl-substituted
series of the bismuth reagents, 1c was the most active whilst the
more bulky mesityl derivative 1i was practically inactive: 4-
methylphenyl (1c: 80%) > 2-methylphenyl (1g: 55%) > 2,4,6-
trimethylphenyl (1i: 4%). It is known that electron-rich aryl bro-
mides (e.g., 4-bromoanisole) are less reactive aryl donors in the
Sonogashira reaction [2]. No noticeable difference in the yield be-
tween electron-rich (1b, c) and electron-deficient (1def) bismu-
thanes was observed in the 4-substituted series of bismuth reagent.
The results indicated that 1f having an electron-deficient aryl group
shows higher reactivity than 1b bearing an electron-rich aryl group.
Generally, the reactivity of aryl halides having electron-
withdrawing groups on the aromatic ring is higher than that of
aryl halides having electron-donating groups, in the Sonogashira
reaction [3]. In the present reaction, this tendency is observed for
triarylbismuthanes (Table 2, entries 11e15). The reaction mecha-
nism of the present Sonogashira-type reaction with triar-
ylbismuthanes 1 is unclear at present. We consider that similar
mechanisms as in the homo-coupling reaction of triar-
ylbismuthanes proposed by Uemura [27], and P-arylation of dialkyl
H-phosphite with triarylbismuthanes under aerobic conditions
proposed by Gao [28], as well as the reaction of terminal alkynes
with aryl trimethoxysilanes proposed by Cheng [14] and with
arylboronic acids as proposed by Bao [11] may be relevant to this
reaction demonstrated here. Possible mechanisms for the reaction
between terminal alkynes and triarylbismuthanes in the formation
of internal alkynes are depicted in Fig. 1. The initial step of the re-
action mechanism is the transmetallation of Pd(II) with triar-
ylbismuthane to afford Ar-Pd-X (A) [27]. A second transmetallation
of A with silver acetylide (B) follows to afford an Ar-Pd-alkyne in-
termediate (C), which then undergoes reductive elimination to form
the coupling products (D) and a Pd(0) species. The Pd(0) species is
oxidized by the silver cation, and Pd(II) is regenerated. An alterna-
tive mechanism path way would involve the generation of Pd(0)
species by the reaction of Pd(OAc)2 with the solvent, substrates and/
or base, followed by the oxidative addition of Ar3Bi to the Pd(0)
species to give ArPdBi complex (E) [28]. Next, transmetallation with
B and reductive elimination would afford the coupling products.
3. Conclusion
In conclusion, we found that triarylbismuthanes are a new class
of arylating agents for a Sonogashira-type coupling reaction under
aerobic conditions. Under mild conditions, all three aryl groups on
the bismuth reagent take part in the reaction, and bismuthanes
with various electron-donating and electron-withdrawing func-
tional groups afford the corresponding cross-coupling products in
satisfactory yields. Studies on the mechanism of this reaction, and
reactions of triarylbismuthanes with other coupling partners, are in
progress.
4. Experimental
4.1. General
Melting points measurements were conducted on a Yanagimoto
micro melting point hot-stage apparatus (MPeS3) and reported as
uncorrected values. 1H NMR (TMS:
d
: 0.00 as an internal standard),
: 77.00 as an internal standard) and 19F NMR
: 0.00 as an internal standard) spectra were recorded on
13C NMR (CDCl3:
(CFCl3:
d
d
JEOL JNMeECA400 (400 MHz, 100 MHz and 376 MHz respectively)
spectrometers in CDCl3. Mass spectra were obtained on a JEOL JMP-
DX300 instrument (70 eV, 300 mA). All chromatographic separa-
tions were accomplished with Silica Gel 60N (Kanto Chemical Co.,
Inc.). Thin-layer chromatography (TLC) was performed with
MachereyeNagel Pre-coated TLC plates Sil G25 UV254. Terminal
alkynes 9 were purchased from Wako Pure Chemical Industries Ltd.
and TCI Fine Chemicals, Japan. Triphenylbismuthane (1a) and tri(o-
tolyl)bismuthane (1g) were purchased from TCI Fine Chemicals,
Japan, and other triarylbismuthanes such as 1b-d [29], 1e [30], 1f
[31], 1h [29], and 1i [32] were prepared according to the reported
procedures.
4.2. Reaction of terminal alkynes with triarylbismuthanes
To a solution of alkyne (9: 1.5 mmol) and triarylbismuthane (1:

M. Matsumura et al. / Journal of Organometallic Chemistry 794 (2015) 70e75
73
Table 2
Pd-catalyzed Sonogashira-type coupling of triarylbismuthanes 1 with alkynes 9a.
Entry
1
Ar3Bi
Ar
Alkyne
Time (h)
Product
Yield (%)b
1a
9b
2
12:85
13:90
14:82
15:78
16:65
17:66
18:68
19:52
20:0
2
9c
9d
9e
9f
2
6
3
4
24
24
24
24
24
24
24
5
6
9g
9h
9i
7
8
9
9j
10
9k
21:0
11
12
13
14
15
16
1b
1c
1d
1e
1f
9a
6
4
12:80
13:83
14:77
22:82
15:76
23:55
2
2
2
1g
24
17
18
1h
1i
24
24
24:42
25:4
a
1 (0.5 mmmol), 9 (1.5 mmol), Pd(OAc)2 (0.025 mmol), K3PO4 (3 mmol), AgF (3 mmol).
Isolated yield. The yield 100% corresponds to the involvement of three aryl groups on 1.
b
0.5 mmol) in CH3CN (5 mL) was added Pd(OAc)2 (0.025 mmol)
followed by K3PO4 (3 mmol) and AgF (3 mmol). The reaction
mixture was stirred at room temperature under an air atmosphere
for the indicated time (2e12 h) until complete consumption of the
starting material, as monitored by TLC and GC. After dilution with
CH2Cl2 (20 mL) and water (20 mL), the reaction mixture was
separated, and the aqueous layer was extracted with CH2Cl2
(20 mL ꢀ 2). The combined organic layers were washed with brine,
dried over anhydrous MgSO4, filtered and concentrated under
reduced pressure. The residue was purified by column chroma-
tography on silica gel to give the aryl alkyne (10, 12e19, 22e25).
The products were confirmed by comparison of their NMR data and
mass spectra with literature data.
1,2-Diphenylethyne (10) [12]: Colorless prisms. mp 60e62 ꢁC
(from MeOH). 1H NMR (400 MHz, CDCl3)
d
: 7.36e7.43 (6H, m,
AreH), 7.58e7.67 (4H, m, AreH); 13C NMR (100 MHz, CDCl3)
d: 89.4,

74
M. Matsumura et al. / Journal of Organometallic Chemistry 794 (2015) 70e75
Fig. 1. Possible mechanism.
123.2, 128.2, 128.3, 131.6. LR-MS m/z: 178 (Mþ).
80.7, 86.0, 119.6, 128.5, 130.6, 133.0, 154.1. LR-MS m/z: 174 (Mþ).
1-Methoxy-4-(phenylethynyl)benzene (12) [12]: Colorless prisms.
Ethyl 4-(phenylethynyl)benzoate (22) [34]: Yellow prisms. mp
mp 55e57 ꢁC (from MeOH). 1H NMR (400 MHz, CDCl3)
d
: 3.82 (3H,
77e79.5 ꢁC (from hexane). 1H NMR (400 MHz, CDCl3)
d: 1.40 (3H, t,
s, OCH3), 6.87 (2H, d, J ¼ 8.7 Hz, AreH), 7.30e7.35 (3H, m, AreH),
J ¼ 7.0 Hz, CH3), 4.39 (2H, q, J ¼ 7.0 Hz, CH2), 7.36e7.37 (3H, m,
7.47 (2H, d, J ¼ 8.7 Hz, AreH), 7.50e7.52 (2H, m, AreH); 13C NMR
AreH), 7.54e7.60 (4H, m, AreH), 8.03 (2H, d, J ¼ 8.2 Hz, AreH); 13
C
(100 MHz, CDCl3)
d
55.3, 88.1, 89.4, 114.0, 115.4, 123.6, 127.9, 128.3,
NMR (100 MHz, CDCl3) d: 14.3, 61.1, 88.7, 92.2, 122.7, 127.9, 128.4,
131.4, 133.0, 159.6. LR-MS m/z: 208 (Mþ).
128.7, 129.5, 129.8, 131.4, 131.7, 166.1. LR-MS m/z: 250 (Mþ).
1-Methyl-2-(phenylethynyl)benzene (23) [12]: Colorless oil. 1H
NMR (400 MHz, CDCl3) : 2.52 (3H, s, CH3), 7.16e7.25 (3H, m,
AreH), 7.33e7.37 (3H, m, AreH), 7.49e7.55 (3H, m, AreH); 13C NMR
1-Methyl-4-(phenylethynyl)benzene (13) [12]: Colorless prisms.
mp 67e69 ꢁC (from hexane). 1H NMR (400 MHz, CDCl3)
d
: 2.37 (3H,
d
s, CH3), 7.16 (2H, d, J ¼ 7.8 Hz, AreH), 7.32e7.34 (3H, m, AreH), 7.43
(2H, d, J ¼ 7.8 Hz, AreH), 7.52e7.53 (2H, m, AreH); 13C NMR
(100 MHz, CDCl3) d: 20.7, 88.3, 93.3, 123.0, 123.5, 125.6, 128.1, 128.3,
(100 MHz, CDCl3)
d
: 21.5, 88.7, 89.5, 120.2, 123.5, 128.0, 128.3, 129.1,
128.3, 129.4, 131.5, 131.8, 140.1. LR-MS m/z: 192 (Mþ).
131.5, 131.5, 138.4. LR-MS m/z: 192 (Mþ).
1-(Phenylethynyl)naphthalene (24) [12]: Colorless oil. 1H NMR
1-Chloro-4-(phenylethynyl)benzene (14) [12]: Colorless prisms.
(400 MHz, CDCl3)
d
: 7.35e7.42 (3H, m, AreH), 7.46 (1H, t, J ¼ 7.0 Hz,
mp 80e81.5 ꢁC (from MeOH). 1H NMR (400 MHz, CDCl3)
d:
AreH), 7.53 (1H, t, J ¼ 6.8 Hz, AreH), 7.59 (1H, t, J ¼ 6.8 Hz, AreH),
7.65 (2H, d, J ¼ 6.9 Hz, AreH), 7.76 (1H, t, J ¼ 7.3 Hz, AreH), 7,84 (2H,
t, J ¼ 8.3 Hz, AreH), 8.44 (1H, d, J ¼ 8.3 Hz, AreH); 13C NMR
7.30e7.36 (5H, m, AreH), 7.44e7.47 (2H, m, AreH), 7.50e7.53 (2H,
m, AreH); 13C NMR (100 MHz, CDCl3)
: 88.2, 90.3, 121.8, 122.9,
128.4, 128.5, 128.7, 131.6, 132.8, 134.3. LR-MS m/z: 212 (Mþ).
1-(Phenylethynyl)-4-(trifluoromethyl)benzene (15) [12,33]:
Colorless prisms. mp 105e106 ꢁC (from MeOH). 1H NMR (400 MHz,
d
(100 MHz, CDCl3) d: 87.5, 94.3, 120.9, 123.4, 125.3, 126.2, 126.4,
126.8, 128.3, 128.4, 128.4, 128.7, 130.4, 131.7, 133.2, 133.3. LR-MS m/
z: 228 (Mþ).
CDCl3)
d
: 7.36e7.38 (3H, m, AreH), 7.54e7.56 (2H, m, AreH), 7.60
1,3,5-Trimethyl-2-(phenylethynyl)benzene (25) [36]: Colorless
(2H, d, J ¼ 8.7 Hz, AreH), 7.63 (2H, d, J ¼ 8.7 Hz, AreH); 13C NMR
prisms. mp 35e36 ꢁC (from MeOH). 1H NMR (400 MHz, CDCl3)
d:
(100 MHz, CDCl3)
d
: 87.9, 91.7, 122.6, 139.0 (J ¼ 263.5 Hz), 125.3
2.29 (3H, s, CH3), 2.50 (6H, s, CH3), 6.91 (2H, s, AreH), 7.27e7.37 (3H,
(J ¼ 3.3 Hz), 127.1, 128.4, 128.8, 129.9 (J ¼ 32.8 Hz), 131.7, 131.8; 19
F
m, AreH), 7.49e7.53 (2H, m, AreH); 13C NMR (100 MHz, CDCl3)
d:
NMR (376 MHz, CDCl3)
d
: ꢂ62.8. LR-MS m/z: 246 (Mþ).
21.0, 21.3, 87.3, 97.0, 120.0, 124.0, 127.6, 127.9, 128.3, 131.3, 137.8,
3-(Phenylethynyl)thiophene (16) [34]: Colorless prisms. mp
140.1. LR-MS m/z: 220 (Mþ).
47e49 ꢁC (from hexane). 1H NMR (400 MHz, CDCl3)
(5H, m, AreH), 7.50e7.53 (2H, m, AreH); 13C NMR (100 MHz, CDCl3)
d: 7.19e7.37
Acknowledgments
d
: 84.5, 88.9, 122.3, 123.2, 125.3, 128.2, 128.3, 128.6, 129.9, 131.5. LR-
MS m/z: 184 (Mþ).
This research was supported by a research grant from Institute
of Pharmaceutical Life Sciences, Aichi Gakuin University and
Hokuriku University.
(1-Cyclohexenylethynyl)benzene (17) [35]: Colorless oil. 1H NMR
(400 MHz, CDCl3)
d: 1.60e1.71 (4H, m, CH2), 2.14e2.23 (4H, m, CH2),
6.19e6.21 (1H, m, C]CH), 7.25e7.43 (5H, m, AreH); 13C NMR
(100 MHz, CDCl3) d: 21.5, 22.3, 25.7, 29.2, 86.7, 91.2, 120.7, 123.8,
References
127.7, 128.2, 131.4, 135.1. LR-MS m/z: 182 (Mþ).
1-Phenyl-1-octyne (18) [35]: Colorless oil. 1H NMR (400 MHz,
ꢀ
[1] R. Chinchilla, C. Najera, Chem. Rev. 107 (2007) 874e922.
[2] H. Doucet, J.-C. Hierso, Angew. Chem. Int. Ed. 46 (2007) 834e871.
[3] E. Negishi, L. Anastasia, Chem. Rev. 103 (2003) 1979e2017.
[4] K. Sonogashira, in: E. Negishi (Ed.), Handbook of Organopalladium Chemisty
for Organic Synthesis, Wiley-Interscience, New York, 2002, pp. 493e529.
[5] For a seminal publication of Sonogashira reaction: K. Sonogashira, Y. Tohda,
N. Hagihara Tetrahedron Lett. 16 (1975) 4467e4470.
[6] P. Siemsen, R.C. Livingston, F. Diederich, Angew. Chem. Int. Ed. 39 (2000)
2632e2657.
[7] A.S. Batsanov, J.C. Collings, I.J.S. Fairlamb, J.P. Holland, J.A.K. Howard, Z. Lin,
T.B. Marder, A.C. Parsons, R.M. Ward, J. Zhu, J. Org. Chem. 70 (2005) 703e706.
[8] G. Zou, J. Zhu, J. Tang, Tetrahedron Lett. 44 (2003) 8709e8711.
[9] F. Yang, Y. Wu, Eur. J. Org. Chem. (2007) 3476e3479.
CDCl3)
d
: 0.90 (3H, t, J ¼ 7.3 Hz, CH3), 1.29e1.36 (4H, m, CH2),
1.42e1.49 (2H, m, CH2), 1.53e1.64 (2H, m, CH2), 2.40 (2H, t,
J ¼ 7.3 Hz, CH2), 7.24e7.30 (3H, m, AreH), 7.37e7.40 (2H, m, AreH);
13C NMR (100 MHz, CDCl3)
d: 14.0, 19.4, 22.5, 28.6, 28.7, 31.4, 80.5,
90.5, 124.1, 127.4, 128.2, 131.5. LR-MS m/z: 186 (Mþ).
Ethyl 3-phenylpropiolate (19) [9,11]: Colorless oil. 1H NMR
(400 MHz, CDCl3)
J ¼ 6.8 Hz, CH2), 7.36e7.39 (2H, m, AreH), 7.43e7.47 (1H, m, AreH),
7.58e7.60 (2H, m, AreH); 13C NMR (100 MHz, CDCl3)
: 14.1, 62.1,
d: 1.36 (3H, t, J ¼ 6.8 Hz, CH3), 4.30 (2H, q,
d

M. Matsumura et al. / Journal of Organometallic Chemistry 794 (2015) 70e75
75
[10] M.-B. Zhou, W.-T. Wei, Y.-X. Xie, Y. Lei, J.-H. Li, J. Org. Chem. 75 (2010)
1921e1924.
5635e5642.
[24] M.L.N. Rao, D.N. Jadhav, P. Dasgupta, Org. Lett. 12 (2010) 2048e2051.
[11] X. Nie, S. Liu, Y. Zong, P. Sun, J. Bao, J. Organomet. Chem. 696 (2011)
1570e1573.
[25] D.V. Moiseev, Y.B. Malysheva, A.S. Shavyrin, Y.A. Kurskii, A.V. Gushchin,
J. Organomet. Chem. 690 (2005) 3652e3663.
[12] L. Lu, P. Chellan, G.S. Smith, X. Zhang, H. Yan, Tetrahedron 70 (2014)
5980e5985.
[13] M. Zhu, Z. Zhou, R. Chen, Synthesis (2008) 2680e2682.
[14] Z. Ye, M. Liu, B. Lin, H. Wu, J. Ding, J. Cheng, Tetrahedron Lett. 50 (2009)
530e532.
[26] S.-K. Kang, H.-C. Ryu, S.-W. Lee, Synth. Commun. 31 (2001) 1027e1034.
[27] T. Ohe, T. Tanaka, M. Kuroda, C.S. Cho, K. Ohe, S. Uemura, Bull. Chem. Soc. Jpn.
72 (1999) 1851e1855.
[28] T. Wang, S. Sang, L. Liu, H. Qiao, Y. Gao, Y. Zhao, J. Org. Chem. 79 (2014)
608e617.
[15] H. Suzuki, Y. Matano (Eds.), Organobismuth Chemistry, Elsevier, Amsterdam,
2001.
[29] S. Combes, J.-P. Finet, Synth. Commun. 26 (1996) 4569e4575.
[30] T. Murafuji, K. Nishio, M. Nagasue, A. Tanabe, M. Aono, Y. Sugihara, Synthesis
(2000) 1208e1210.
[31] T. Arnauld, D.H.R. Barton, J.-F. Normant, J. Org. Chem. 64 (1999) 3722e3725.
[32] Y. Matano, M. Kinoshita, H. Suzuki, Bull. Chem. Soc. Jpn. 65 (1992) 3504e3506.
[33] Y.-T. Hung, M.-T. Chen, M.-H. Huang, T.-Y. Kao, Y.-S. Liu, L.-C. Liang, Inorg.
Chem. Front. 1 (2014) 405e413.
[34] J.R. Harjani, T.J. Abraham, A.T. Gomez, M.T. Garcia, R.D. Singer, P.J. Scammells,
Green. Chem. 12 (2010) 650e655.
[35] S. Atobe, M. Sonoda, Y. Suzuki, H. Shinohara, T. Yamamoto, A. Ogawa, Chem.
Lett. 40 (2011) 925e927.
[16] Y. Matano, Chapter 14, in: H. Yamamoto, K. Oshima (Eds.), Main Group Metals
in Organic Synthesis, vol. 2, Wiley-VCH, Weinheim, 2004, pp. 753e811.
[17] S. Maeda, Chapter 19, in: S. Patai (Ed.), The Chemistry of Organic Arsenic,
Antimony and Bismuth Compouds, Wiley, New York, 1994, pp. 725e759.
[18] S. Condon, C. Pichon, M. Davi, Org. Prep. Proced. Int. 46 (2014) 89e131.
[19] S. Shimada, M.L.N. Rao, Top. Curr. Chem., in: T. Ollevier (Ed.), Bismuth-
mediated Organic Reactions, vol. 311, Springer, Berlin, 2012, pp. 199e228.
[20] M.L.N. Rao, R.J. Dhanorkar, Tetrahedron 71 (2015) 338e349.
[21] M.L.N. Rao, A. Kumar, Tetrahedron 70 (2014) 6995e7005.
[22] P. Petiot, A. Gagnon, Eur. J. Org. Chem. (2013) 5282e5289.
[23] O. Yamazaki, T. Tanaka, S. Shimada, Y. Suzuki, M. Tanaka, Synlett, 2004
[36] J. Moon, M. Jang, S. Lee, J. Org. Chem. 74 (2009) 1403e1406.