Palladium-catalyzed cross-coupling reaction of ethynylstibanes with organic halides

Article abstract of DOI:10.1016/j.jorganchem.2005.03.021

The reaction of ethynylstibanes (1a-g) with vinyl halides or triflate in the presence of a palladium catalyst led to the formation of cross-coupling products (5a-g, 10-12) in good to moderate yield, along with homo-coupling products (6a-g). A similar reaction of ethynyldiphenylstibane (1a) with aryl iodides (13a-i) also gave cross-coupling products (14a-i), although the yields were relatively low. The yields of the cross-coupling products were highly dependent on the nature of the solvent employed, and good results were obtained when the reaction was carried out in HMPA or amines such as diethylamine and morpholine. The results imply that HMPA and amine used as solvents facilitate transmetallation of the ethynyl group on 1 to the palladium by intermolecular coordination between antimony and oxygen (for HMPA) or nitrogen (for amine).

Full text of DOI:10.1016/j.jorganchem.2005.03.021

Journal of Organometallic Chemistry 690 (2005) 2956–2966
www.elsevier.com/locate/jorganchem
Palladium-catalyzed cross-coupling reaction of ethynylstibanes
with organic halides
*
Naoki Kakusawa, Kouichiro Yamaguchi, Jyoji Kurita
Faculty of Pharmaceutical Sciences, Hokuriku University, Kanagawa-machi, Kanazawa 920-1181, Japan
Received 10 August 2004; revised 8 March 2005; accepted 8 March 2005
Available online 29 April 2005
Abstract
The reaction of ethynylstibanes (1a–g) with vinyl halides or triflate in the presence of a palladium catalyst led to the formation of
cross-coupling products (5a–g, 10–12) in good to moderate yield, along with homo-coupling products (6a–g). A similar reaction of
ethynyldiphenylstibane (1a) with aryl iodides (13a–i) also gave cross-coupling products (14a–i), although the yields were relatively
low. The yields of the cross-coupling products were highly dependent on the nature of the solvent employed, and good results were
obtained when the reaction was carried out in HMPA or amines such as diethylamine and morpholine. The results imply
that HMPA and amine used as solvents facilitate transmetallation of the ethynyl group on 1 to the palladium by intermolecular
coordination between antimony and oxygen (for HMPA) or nitrogen (for amine).
Ó 2005 Elsevier B.V. All rights reserved.
Keywords: Antimony; Cross-coupling; Intermolecular coordination; Ethynylstibane; Vinyl halide; Aryl halide
1. Introduction
ported [4]. However, contrary to the prevailing use of
inorganic antimony compounds for Lewis acid, super
acid, antimony metal alloy, and anti-flammable materi-
als, studies on organoantimony compounds as a novel
synthetic reagent are relatively underdeveloped. Most of
them dealt with highly reactive but less stable pentavalent
or hypervalent antimony compounds [5]. From the view-
point of practical use of organoantimony compounds as a
synthetic reagent, it is desirable for them to be relatively
stable, easy to prepare and to handle. Trivalent organ-
oantimony compounds (stibanes) are stable enough to
tolerate practical handling, less harmful, and not so
expensive. So it is worth investigating stibanes as novel
practical organic reagents [6].
As a part of our continuing research on making use of
stibanes as practical organic reagents, we have previously
reported the palladium-catalyzed ethynylation of acyl
chloride using ethynylstibanes [7]. Thus, acyl chlorides
and ethynyldiphenylstibanes were coupled by use of 5
mol% of commercially available palladium reagents to
give ethynylketones in good to excellent yields. The
Recent researches on typical heavier elements have dis-
closed a variety of reactions which so far are believed to be
extraordinary to synthetic organic chemists [1]. Different
from the typical lower elements such as carbon, nitrogen,
and oxygen, the heavier elements have lower electronega-
tivity and relatively larger atomic radii which form longer
and weaker bonds between them and other elements [2].
These properties make it facile for these compounds to
form highly reactive hypervalent species with hetero
atoms such as nitrogen, oxygen, sulfur and so on. Taking
advantage of these characters, much attention has been
directed toward utilization of these compounds as novel
synthetic reagents, and a variety of hetero atoms are
now commonly employed in transition-metal catalyzed
coupling reactions [3]. Many attempts to apply organoan-
timony compounds to a synthetic reagent are also re-
*
Corresponding author. Tel.: +81 76 229 1165; fax: +81 76 229 2781.
E-mail address: j-kurita@hokuriku-u.ac.jp (J. Kurita).
0022-328X/$ - see front matter Ó 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.03.021

N. Kakusawa et al. / Journal of Organometallic Chemistry 690 (2005) 2956–2966
2957
reaction was thought to proceed by the classical Stille-
type catalytic cycle [8]. In order to improve the generality
of the reaction, cross-coupling with aryl and vinyl iodides
was investigated, and full details of these reactions includ-
ing preparation of ethynylstibanes are described here.
ethynylstibanes were prepared by the condensation of
diphenylantimony bromide [11] with appropriate lith-
ium acetylides [12]. Thus, diphenylantimony bromide,
prepared from redistribution of a 2:1 mixture of triphe-
nylantimony and tribromoantimony, was reacted with
lithium acetylides generated from the corresponding
acetylene derivatives and butyllithium. Arylethynyl, alk-
ylethynyl, and silylethynyl compounds (1a–g) were ob-
tained in moderate to good yields (Table 1). Each
compound was so stable such that it could be purified
on silica gel column chromatography and kept in a
refrigerator for over several years.
2. Results and discussion
2.1. Preparation of ethynylstibanes
Highly reactive pentavalent organoantimony com-
pounds easily underwent either reductive homo-coupling
or cross-coupling reaction with organic halides under
transition metals [5]. However, trivalent stibanes have
been thought to be less reactive in these classes of reac-
tion. Asano et al. [9] have first reported that treatment
of triphenylantimony with styrene resulted in cross-cou-
pling reaction to afford trans-stilbene, but their reaction
required a stoichiometric amount of the palladium re-
agent. Barton et al. [10] have also performed a ligand cou-
pling reaction of triarylstibanes with acyl halides using a
stoichiometric amount of palladium. Uemura and
coworkers [6b] have first demonstrated a catalytic cross-
coupling reaction of triarylstibanes with enones to pro-
duce b-arylated ketones in the presence of a palladium
catalyst, although the reaction required 2 equimolar
amounts (on the bases of SbPh3) of AgOAc as an oxidant
and an acidic condition. They also developed the same
type of reaction using phenylantimony chlorides instead
of the triarylstibane under an aerobic condition [6a].
We have recently reported that ethynylstibanes could
be isolated as air-stable compounds [7]. Taking the high
reactivity of the ethynyl group in the Stille reaction and
other cross-coupling reaction into consideration [8d],
ethynylation of organic halides under palladium catalyst
might be possible even by use of the so-called less
reactive trivalent stibanes. From this point of view,
2.2. Cross-coupling reaction of ethynylstibanes with vinyl
halides
It is well documented that 1,3-enynes and aryl acety-
lenes are an important building-block for a variety of
biologically active substances, medicinals, liquid crystals
and conductive polymers, and various methods to pre-
pare them have been investigated [13,14]. We considered
that cross-coupling reaction of ethynylstibanes with vi-
nyl halides and aryl halides should be another synthetic
approach to these compounds.
In this context, we initially performed the reaction of
ethynylstibanes (1) and cyclopentenyl derivatives, such
as cyclopentenyl iodide (2), bromide (3) and triflate
(4), to compare the reactivity of the leaving group using
5 mol% of dichlorobis(triphenylphosphine)palladium
[PdCl2(PPh3)2] as a catalyst in hexamethylphosphoramide
(HMPA) at 80 °C, (Table 2, entry 1–3). The expected
enyne compound (5a) was obtained in good yields when
the iodide (2) and triflate (4) were employed as a cou-
pling partner. However, the vinyl bromide (3) was found
to be unreactive toward the cross-coupling reaction and
the major product was 1,3-diyne (6a) derived from
homo-coupling reaction of the ethynyl group on 1. A
survey of solvents revealed that the reaction took place
Table 1
Preparation of ethynyldiphenylstibanes 1a–g
Li
R
heat
Ph2Sb
R
2 Ph3Sb
SbBr3
Ph2SbBr
at 90˚C
1a-g
( 2 : 1 )
R
Yield of 1 (%)a
Appearance
a: Phenyl
73
64
74
64
78
69
78
m.p. 53–55 °Cb,c
m.p. 63–64 °Cc
m.p. 62–63 °Cc
m.p. 42–43 °Cc
Colorless oil
b: p-Tolyl
c: p-Anisyl
d: p-Fluorophenyl
e: n-Butyl
f: t-Butyl
Colorless oil
Colorless oil
g: TMS
a
Isolated yield.
Literature [11], m.p. 84–86 °C.
Recrystallized from ether–ethanol.
b
c

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N. Kakusawa et al. / Journal of Organometallic Chemistry 690 (2005) 2956–2966
Table 2
Reaction of diphenylphenylethynylstibane 1a with cyclopentene derivatives 2–4 using a variety of Pd-catalysts and solventsa
Pd cat.
Ph
Ph
Ph2Sb
Ph
Ph
X
Solvent
6a
5a
1a
2-4
2 : X = I
3 : X = Br
4 : X = OTf
Entry
Cyclopentene deriv. (X)
Pd-Cat.
Solvent
HMPA
Temp. (°C)
Time (h)
Yield (%)b
5a
6a
1
2
3
2: I
3: Br
4: OTf
PdCl2(PPh3)2
PdCl2(PPh3)2
80
1.0
3.5
1.0
90
0.3
80
9
40
9
4
5
2: I
HMPA
25
80
80
80
80
55
80
80
80
80
20.0
1.5
2.0
3.0
2.0
21.0
1.0
1.0
1.0
1.0
87
15
5
9
42
66
41
39
11
9
1,2-Dichloroethane
Acetonitril
Benzene
6
7
24
28
78
87
64
52
54
8
1,4-Dioxane
Diethylamine
Morpholine
NMP
9
10
11
12
13
24
37
27
TMU
DMPU
14
15
16
17
a
2: I
PdCl2(PhCN)2
Pd(OAc)2
HMPA
80
1.0
60
53
29
53
38
43
41
44
PdCl2(CH2 = CHCH3)2
PdCl2
1a (1 mmol), 2–4 (1.5 mmol), Pd-Cat. (5 mol%), solvent (10 ml).
Determined by GLC. The yield of 6a was calculated on the bases of that 0.5 equimolar amounts of 6a to 1a correspond to 100% yield.
b
efficiently in amines and HMPA, whereas halogenated
solvents, ethereal solvents, hydrocarbons, and aprotic
polar solvents such as 1-methyl-2-pyrrolidinone
(NMP), tetramethylurea (TMU), and N,N0-dimethyl-
propyleneurea (DMPU) gave inferior results (Table 2,
entry 5–13). Several easily available palladium catalysts
were also screened (Table 2, entry 14–17). The results
showed that the palladium with a phosphine ligand
was preferable for effective transmetallation of the ethy-
nyl group from antimony to palladium. Without phos-
phine ligands, palladium might coordinate with stibane
which can act as a mild palladium ligand [15]. A
tightly-coordinated phosphine ligand stabilizes the
palladium and might prevent it from undesirable
coordination with antimony. These reactions were
highly substituent-selective and only the ethynyl group
was transferred from 1a to form 1,3-enynes (5a) and aryl
acetylenes (6a), indicating that the phenyl groups on 1a
work as dummy ligands in the present reaction. These
results are comparable with that the ethynyl moiety in
ethynylstannanes is more reactive than aryl, vinyl
and alkyl groups in Stille-coupling reaction [8a].
Consequently, the best result was obtained up to now
when the reaction was carried out in HMPA with
PdCl2(PPh3)2.
In order to prove the generality of this cross-coupling
reaction, ethynyldiphenylstibanes (1b–g) were reacted
with 1-iodocyclopentene (2) and the results are shown
in Table 3. The iodine function was displaced effectively
with an arylethynyl, alkylethynyl and silylethynyl group
to afford the corresponding 1,3-enyne compounds (5b–
g) in good to moderate yields. Reaction of phen-
ylethynyldiphenylstibane (1a) with several vinyl iodides
(7–9) also brought about the expected cyclic (10) and
acyclic enyne compounds (11, 12) as major products in
moderate yields (Table 4).
2.3. Cross-coupling reaction of ethynylstibanes with aryl
halides
Next, the reaction of the ethynylstibane (1a) with a
variety of aryl halides was investigated to disclose the
difference in the reactivity between vinyl halides and aryl
halides, and the results are summarized in Table 5.
Phenylethynylstibane (1a) and iodobenzene (13a) were
reacted using PdCl2(PPh3)2 catalyst in various solvents
(Table 5, entry 1–8). In the reaction with 13a, longer
reaction time was required to complete the reaction even
in the presence of 10 mol% of the palladium catalyst.
These results showed that the reactivity of 13a was lower

N. Kakusawa et al. / Journal of Organometallic Chemistry 690 (2005) 2956–2966
2959
Table 3
Reaction of ethynyldiphenylstibanes 1a–g with 1-iodocyclopentene 2a
PdCl2(PPh3)2
I
R
R
R
Ph2Sb
R
HMPA, 80˚C,1h
5a-g
6a-g
1a-g
2
R
Yield (%)b
5
6
a: Phenyl
b: p-Tolyl
c: p-Anisyl
90
87
69
85
70
75
64
9
9
21
8
d: p-Fluorophenyl
e: n-Butyl
f: t-Butyl
g: TMS
9
13
15
a
1a–g (1 mmol), 2 (1.5 mmol), Pd-Cat. (5 mol%), HMPA (10 ml).
Determined by GLC. The yield of 6 was calculated on the bases of that 0.5 equimolar amounts of 6a–g to 1a–g correspond to 100% yield.
b
Table 4
Reaction of ethynylstibanes 1a with vinyl iodides 7–9a
PdCl2(PPh3)2
Ph2Sb
Ph
R'
7-9
I
R'
Ph
Ph
Ph
HMPA, 80˚C, 1h
10-12
1a
6a
Vinyl halide R0–I
Product 10–12
Yield (%)b
10–12
67
6a
30
7
10
Ph
I
41
63
39
30
n-Bu
11
8
9
n-Bu
Ph
I
Ph
12 Ph
I
Ph
a
1a (1 mmol), 7–9 (1.5 mmol), Pd-Cat. (5 mol%), HMPA (10 ml).
Determined by GLC. The yield of 6a was calculated on the bases of that 0.5 equimolar amounts of 6a to 1a correspond to 100% yield.
b
than that of the vinyl iodides. A remarkable solvent ef-
fect, namely amines and HPMA were superior to other
solvents, was observed as in the case of the former reac-
tion with vinyl halides. We considered that amine and
HMPA used as solvents would activate the Sb–C(sp)
bond by intermolecular coordination between the un-
shared electron pair on nitrogen or oxygen and the anti-
mony atom on 1a. We have already reported that
intramolecular interaction between the nitrogen and
antimony in 12-arylethynyl-6-methyl-5,6,7,12-tetrahyd-
rodibenz[c,f][1,5]azastibocines led to an elongation of
the Sb–C(sp) bond and facilitated easier cross-coupling
reaction between the ethynyl group on antimony and or-
ganic halides [16]. The following evidence should also
support this interpretation. We have recently reported
that several triarylstibanes bearing amine moiety, e.g.,
2-(N,N-dimethylaminobenzyl)diphenylstibane, have Sb–N
intramolecular coordination and the coordination
brings about marked lowering of oxidation potential
of the antimony atom. Similar effect on decreasing the
potential was observed in a mixture of triphenylstibane
and N,N-dimethylbenzylamine, which was never de-
tected in a solution of triphenylstibane or N,N-dimethyl-
benzylamine alone [17]. These results indicate the
existence of intermolecular interaction between the anti-
mony and nitrogen atoms in this system. Similar Sb–N
and Sb–O intermolecular coordinations which bring
about Sb–C(sp) bond activation may occur when amine

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N. Kakusawa et al. / Journal of Organometallic Chemistry 690 (2005) 2956–2966
Table 5
Reaction of ethynylstibane 1a with aryl iodides 13a–ia
PdCl2(PPh3)2
Ar
Ph
Ar
I
Ph
Ph
Ph2Sb
Ph
Solvent, Heat 24 h
14a-i
1a
Ar: 13a–i
13a-i
6a
Entry
Solvent
Temp. (°C)b
Yield (%)c
14
6a
1
2
3
4
5
6
7
8
13a: Phenyl
1,2-Dichloroethane
THF
80
60
80
80
80
55
80
80
16
20
32
24
33
49
46
37
47
60
54
32
23
21
31
51
Acetonitrile
Benzene
Diisopropylamine
Diethylamine
Morpholine
HMPA
9
10
11
12
13
14
15
16
a
13b: p-Anisyl
13c: o-Tolyl
13d: p-Tolyl
Diethylamine
55
35
30
34
43
46
77
73
87
25
20
20
7
13e: p-Fluorophenyl
13f: p-Acetylphenyl
13g: o-Nitrophenyl
13h: m-Nitrophenyl
13i: p-Nitrophenyl
7
11
20
5
1a (1 mmol), 13a–i (1.5 mmol), Pd-Cat. (10 mol%), solvent (5 ml), 24 h.
Bath temperature.
Determined by GLC. The yield of 6a was calculated on the bases of that 0.5 equimolar amounts of 6a to 1a correspond to 100% yield.
b
c
and HMPA is employed as solvent in the present reac-
tion, although no evidence of the Sb–O coordination in
the stibane–HMPA system has not been obtained at pres-
ent. Also apparent is that substituents on aryl iodides (13)
exhibit a distinctive effect in the coupling reaction. Aryl
iodides with electron-withdrawing groups gave better re-
sults than those with electron-donating groups similar to
other palladium-catalyzed coupling reactions (Table 5,
entry 9–16). The electron-withdrawing group should
assist the oxidative addition of aryl halides to the
phosphine-ligated, electron-rich palladium(0) [8].
The palladium-catalyzed alkynylation is thought to
be initiated by oxidative addition of organic halides
and related electrophiles to Pd(0). The pathways of the
cross-coupling reaction of ethynylstibanes (1) with vinyl
iodides and the homo-coupling reaction of 1 itself in the
N
Ph2Sb E
R-X
L
L
Ph2Sb Pd(II) E
R Pd(II) X
Oxidative
Addition
L
N
N
A
C
L
Ph2Sb E
Ph2Sb E
L
Catalytic cycle (a)
Catalytic cycle (b)
Transmetallation
Ph2Sb X
Pd(0)
L
Transmetallation
Ph2Sb-SbPh2
L
L
Reductive
Eliminatioin
E Pd(II) E
R Pd(II) E
L
L
D
B
E E
E =
R E
R
Fig. 1.

N. Kakusawa et al. / Journal of Organometallic Chemistry 690 (2005) 2956–2966
2961
present reaction are depicted in Fig. 1. When the reactiv-
ity of the halide (R–X) is sufficiently higher than that of
the stibanes, oxidative addition of the halides to Pd(0)
may take place in preference to the reaction with ethy-
nylstibane, as shown in the reaction with vinyl iodides
and aryl iodides bearing electron withdrawing groups.
The Pd(II) complex (A) thus formed results in transmet-
allation with the ethynyl group (E) on 1 to afford Pd(II)
complex (B) which undergoes reductive elimination to
give the cross-coupling product (R–E) via a catalytic cy-
cle (a). The intermolecular coordination of the amine
moiety used as a solvent to the antimony on 1 would
activate the Sb–C(sp) bond and assist the transmetalla-
tion as noted above. When the reactivity of the halides
is relatively low, however, competition for oxidative
addition to Pd(0) will arise between the halides and
the ethynylstibanes, such that the latter should bring
about the homo-coupling product (E–E) via a catalytic
cycle (b), although the evidence for the formation of
Ph2Sb–SbPh2 has so far not been obtained from the
reaction mixture.
spectra were recorded on a JEOL JNM–ECP–500 (500
and 125 MHz) spectrometer in CDCl3 unless otherwise
stated. Mass spectra (MS) and high-resolution mass
spectra (HRMS) were obtained on a JEOL JMS–SX
102A instrument and IR spectra were recorded on a
HORIBA FT–720 instrument. GLC analyses of the
products were made using Shimazu GC–14B. All chro-
matographic separations were accomplished with either
Kieselgel 60 (Merck) or Silica Gel 60N (Kanto Chemical
Co., Inc.). Thin-layer chromatography (TLC) was per-
formed with Macherey-Nagel Pre-coated TLC plates
Sil G25 UV254. All of HMPA including the aqueous solu-
tion of HMPA arose from working up of the reaction
mixture should be collected in a fixed glass bottle and
the contents will be treated by an appropriate company
specialized in the disposal of chemical waste, because
HMPA has been known to be a cancer suspect agent.
4.2. Preparation of ethynyldiphenylstibanes (1a–g)
General procedure. An ether solution (100 ml) of
diphenylantimony(III) bromide [12], synthesized from
redistribution of triphenylstibane (23.5 g, 67 mmol)
and tribromoantimony (12.0 g, 33 mmol) was added
dropwise at 0 °C to an ether solution (100 ml) of lithium
acetylide, prepared from the appropriate acetylene deriv-
atives (100 mmol) and butyllithium (1.53–1.48 M solu-
tion in hexane, 100 mmol). After stirring the mixture at
the same temperature for 2 h, the reaction mixture was
diluted with ether (100 ml) and quenched with water.
The reaction mixture was separated and the aqueous
layer was extracted with ether (50 ml). The combined or-
ganic layer was washed with brine, dried over anhydrous
MgSO4, and concentrated under reduced pressure. The
residue was purified by SiO2 column chromatography
using a mixture of n-hexane and dichloromethane as elu-
ent to afford ethynyldiphenylstibanes (1a–g). The eth-
ynyldiphenylstibanes (1a–g) thus obtained are listed
together with their yields and appearances in Table 1.
3. Conclusion
In summary, we have developed a simple and useful
preparative method for trivalent ethynylstibanes (1a–g)
which are air-stable, easy to handle and can be stored
with no special care. In palladium-catalyzed cross-
coupling of the ethynyldiphenylstibane with vinyl and
aryl iodides, only the ethynyl group on the ethynylsti-
banes reacted to form 1,3-enynes and aryl acetylenes,
and phenyl groups functioned as dummy ligands. As
for a practical ethynylation technique of organic ha-
lides, a variety of useful methods have been published
[3a,18]. Further improvements including reactivity
enhancement of antimony-mediated coupling reactions
with heteroatom–antimony nonbonding interaction are
now in progress and will be reported by us in due
course.
4.2.1. Diphenylphenylethynylstibane (1a)
Anal. Calc. for C20H15Sb: C, 63.70; H, 4.01. Found:
1
C, 63.82; H, 4.18. H NMR (d ppm): 7.29–7.35 (9H,
4. Experimental
m), 7.50–7.52 (2H, m), 7.71–7.34 (4H, m). 13C NMR
(d ppm): 85.6 (s), 111.4 (s), 123.3 (s), 128.2 (d), 128.6
(d), 128.8 (d), 129.0 (d), 132.0 (d), 135.5 (d), 138.1 (s).
MS (EI) m/z: 376 (M+, 77%), 299 (8%), 198 (100%),
178 (96%). IR (cmꢀ1): 2137 (C„C).
4.1. General
All reactions were carried out in pre-dried glassware
under an argon atmosphere. Ether was distilled from
its LiAlH4 suspension and dried over sodium wire. Ele-
mentary combustion analyses were determined by a Ya-
nako CHN CORDER MT–5 and melting points were
taken on a Yanagimoto micro melting point hot-stage
apparatus (MP–S3) and are not corrected. 1H NMR
(TMS: d 0.00 ppm as an internal standard) and 13C
NMR (CDCl3: d 77.00 ppm as an internal standard)
4.2.2. Diphenyl(p-tolylethynyl)stibane (1b)
Anal. Calc. for C21H17Sb: C, 64.49; H, 4.38. Found:
1
C, 64.52; H, 4.41. H NMR (d ppm): 2.34 (3H, s), 7.11
(2H, d, Jp-tol = 7.79 Hz), 7.29–7.35 (6H, m), 7.41 (2H,
d, Jp-tol = 7.79 Hz), 7.71–7.73 (4H, m). 13C NMR (d
ppm): 21.5 (q), 84.9 (s), 111.6 (s), 120.2 (s), 128.8 (d),
128.9 (d), 129.0 (d), 131.9 (d), 135.5(d), 138.2 (s), 138.8

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N. Kakusawa et al. / Journal of Organometallic Chemistry 690 (2005) 2956–2966
(s). MS (EI) m/z: 390 (M+, 67%), 313 (7%), 236 (14%),
198 (78%), 192 (100%). IR (cmꢀ1): 2132 (C„C).
triflate (4), 1.50 mmol] and dichlorobis(triphenylphos-
phine)palladium (35 mg, 0.05 mmol) in HMPA (10 ml)
was heated at 80 °C for 1 h under an argon atmosphere.
After dilution with ether (100 ml) and water (100 ml),
the reaction mixture was separated and the aqueous
layer was extracted with ether (30 ml). The combined or-
ganic layer was washed with water, dried over anhy-
drous MgSO4, and concentrated under reduced
pressure. The crude residue was purified by passing
through SiO2 short column using a mixture of n-hexane
and benzene as eluent to give enyne derivatives (5a–g,
10–12) and 1,3-butadiyne derivatives (6a–g). Yields of
the products were analyzed by GLC (5% SE30, 1.6 M,
column temperature 230 °C) based on benzil (tR = 2.66
min) as an internal standard.
4.2.3. p-Anisylethynyldiphenylstibane (1c)
Anal. Calc. for C21H17OSb: C, 61.96; H, 4.21. Found:
1
C, 62.14; H, 4.37. H NMR (d ppm): 3.79 (3H, s), 6.83
(2H, d, Jp-anisyl = 8.70 Hz), 7.31–7.35 (6H, m), 7.46 (2H,
d, Jp-anisyl = 8.70 Hz), 7.71–7.73 (4H, m). 13C NMR (d
ppm): 55.3 (q), 84.0 (s), 111.5 (s), 113.9 (d), 115.4 (d),
128.8 (d), 128.9 (d), 133.5 (d), 135.5 (d), 138.3 (s), 159.8
(d). MS (EI) m/z: 406 (M+, 53%), 329 (5%), 252 (8%),
208 (100%), 198 (33%). IR (cmꢀ1): 2140 (C„C).
4.2.4. p-Fluorophenylethynylldiphenylstibane (1d)
Anal. Calc. for C20H14FSb: C, 60.80; H, 3.57. Found:
C, 60.72; H, 3.72. 1H NMR (d ppm): 7.00 (2H, dd,
1,2
JH,H = 8.70 Hz,
J
= 8.70 Hz), 7.32–7.37 (6H, m),
1,3
4.3.1. Reaction of diphenylphenylethynylstibane (1a) with
1-iodocyclopentene (2) [19]
H,F
7.49 (2H, dd, JH,H = 8.70 Hz,
J
= 5.50 Hz), 7.70–
H,F
7.72 (4H, m). 13C NMR (d ppm): 85.6 (s), 110.2 (s),
115.5 (dd, 2JF = 21.9 Hz), 119.4 (s), 128.9 (dd,
3JF = 13.4 Hz), 129.0 (d), 133.9 (d, 4JF = 8.6 Hz),
1-Phenylethynylcyclopentene (5a); (tR = 1.27 min),
152.2 mg (91%). Colorless needles (m.p. 82–84 °C, from
ethanol). 1H NMR (d ppm): 1.94 (2H, m), 2.47 (2H, m),
2.54 (2H, m), 6.13 (1H, m), 7.26–7.30 (3H, m), 7.42–7.44
(2H, m). 13C NMR (d ppm): 23.4 (t), 33.4 (t), 36.4 (t),
86.8 (s), 90.4 (s), 123.6 (s), 124.6 (s), 127.9 (d), 128.2
(d), 131.4 (d), 138.1 (d). MS (EI) m/z: 168 (M+, 100%),
153 (32%), 139 (18%), 115 (13%). IR (cmꢀ1): 2202
(C„C), 1671 (C@C). 1,4-Diphenyl-1,3-butadiyne (6a);
(tR = 5.36 min), 18.2 mg (9%). Colorless needles (m.p.
87–88 °C, from ethanol [4] 84–86 °C). 1H NMR (d
ppm): 7.31–7.38 (6H, m), 7.51–7.53 (4H, m). 13C
NMR (d ppm): 73.9 (s), 81.5 (s), 121.8 (s), 128.4 (d),
129.2 (d), 132.5 (d). MS (EI) m/z: 202 (M+, 100%), 174
(4%), 150 (7%), 126 (2%). IR (cmꢀ1): 2148 (C„C).
1
135.5 (d), 138.0 (s), 162.6 (d, JF = 248.0 Hz). MS (EI)
m/z: 394 (M+, 46%), 317 (5%), 273 (42%), 198 (100%).
IR (cmꢀ1): 2144 (C„C).
4.2.5. 1-Hexynyldiphenylstibane (1e)
HR-MS m/z: 356.0446 (Calc. for C18H19Sb:
356.0523). 1H NMR (d ppm): 0.90 (3H, t, J = 6.96
Hz), 1.42–1.58 (4H, m), 2.38 (2H, t, J = 6.96 Hz),
7.29–7.30 (6H, m), 7.66–7.67 (4H, m). 13C NMR (d
ppm): 13.6 (q), 20.1 (t), 21.9 (t), 30.9 (t), 74.6 (s), 113.7
(s), 128.6 (d), 128.8 (d), 135.4 (d), 138.5 (s). MS (EI)
m/z: 356 (M+, 22%), 299 (5%), 279 (7%), 198 (100%).
IR (cmꢀ1): 2152 (C„C).
4.3.2. Reaction of diphenylphenylethynylstibane (1a) with
1-bromocyclopentene (3) [20]
5a, 0.43 mg (0.3%); 6a, 40 mg (40%).
4.2.6. 3,3-Dimethyl-1-butynyldiphenylstibane (1f)
HR-MS m/z: 356.0530 (Calc. for C18H19Sb:
1
356.0525). H NMR (d ppm): 1.30 (9H, s), 7.28–7.33
(6H, m), 7.64–7.69 (4H, m). 13C NMR (d ppm): 31.0
(s), 31.2 (q), 73.1 (s), 122.2 (s), 128.6 (d), 128.8 (d),
135.2 (d), 138.7 (s). MS (EI) m/z: 356 (M+, 29%), 300
(14%), 278 (6%), 198 (100%). IR (cmꢀ1): 2132 (C„C).
4.3.3. Reaction of diphenylphenylethynylstibane (1a) with
1-trifluoromethanesulfonylcyclopentene (4) [21]
5a, 131.9 mg (79%); 6a, 9.5 mg (9.5%).
4.3.4. Reaction of diphenyl(p-tolylethynyl)stibane (1b)
with 1-iodocyclopentene (2)
1-(p-Tolylethynyl)cyclopentene (5b); (tR = 1.80 min),
4.2.7. Trimethylsilylethynyldiphenylstibane (1g)
HR-MS m/z: 372.0284 (Calc. for C17H19SiSb:
1
372.0293). H NMR (d ppm): 0.24 (9H, s), 7.30–7.33
158 mg (87%). Colorless needles (m.p. 92–93 °C, from
1
(6H, m), 7.67–7.69 (4H, m). 13C NMR (d ppm): 0.02
(q), 104.3 (s), 120.4 (s), 128.9 (d), 135.4 (d), 136.2 (d),
138.0 (s). MS (EI) m/z: 372 (M+, 31%), 357 (5%), 275
(8%), 198 (61%). IR (cmꢀ1): 2084 (C„C).
ethanol). H NMR (d ppm): 1.94 (2H, m), 2.32 (3H,
s), 2.46 (2H, m), 2.54 (2H, m), 6.10 (1H, m), 7.10 (2H,
d, Jp-tol = 7.70 Hz), 7.32 (2H, d, Jp-tol = 7.70 Hz). 13C
NMR (d ppm): 21.4 (q), 23.4 (t), 33.3 (t), 36.5 (t), 86.1
(s), 90.6 (s), 120.5 (s), 124.7 (s), 129.0 (d), 131.3 (d),
137.6 (d), 138.0 (s). MS (EI) m/z: 182 (M+, 100%), 167
(79%), 152 (29%), 139 (18%), 115 (17%). IR (cmꢀ1):
2204 (C„C), 1658 (C@C). 1,4-Di(p-tolyl)-1,3-butadiyne
(6b); (tR = 12.28 min), 11 mg (9%). Colorless needles
4.3. Reaction of ethynyldiphenylstibane (1a–g) with vinyl
halides (2, 3, 7–9) or triflate (4)
General procedure. A solution of ethynylstibane (1a–
g, 1.00 mmol), vinyl halides (2, 3, 7–9, 1.50 mmol) [or
1
(m.p. 187–188 °C, from ethanol). H NMR (d ppm):

N. Kakusawa et al. / Journal of Organometallic Chemistry 690 (2005) 2956–2966
2963
2.35 (6H, s), 7.12 (4H, d, Jp-tol = 7.79 Hz), 7.40 (4H, d,
p-tol = 7.79 Hz). 13C NMR (d ppm): 21.6 (q), 73.4 (s),
81.5 (s), 118.8 (s), 129.2 (d), 132.4 (d), 139.5 (s). MS
(EI) m/z: 230 (M+, 100%), 215 (18%), 202 (7%), 189
(5%), 115 (5%). IR (cmꢀ1): 2135 (C„C).
19.1 (t), 22.0 (t), 23.3 (t), 30.9 (t), 33.0 (t), 36.6 (t),
77.7 (s), 91.4 (s), 125.0 (s), 135.8 (d). MS (EI) m/z: 148
(M+, 38%), 133 (13%), 119 (35%), 105 (76%), 91
(100%). IR (cmꢀ1): 2213 (C„C), 1675 (C@C). 5,7-Dod-
ecadiyne (6e); (tR = 0.815 min), 7.1 mg (9%). Colorles
J
1
oil. H NMR (d ppm): 0.91 (6H, t, J = 7.33 Hz), 1.41
4.3.5. Reaction of p-anisylethynyldiphenylstibane (1c)
with 1-iodocyclopentene (2)
(4H, sextet, J = 7.33 Hz), 1.50 (4H, quintet, J = 7.33
Hz), 2.25 (4H, t, J = 7.33 Hz). 13C NMR (d ppm):
13.5 (q), 18.9 (t), 21.9 (t), 30.4 (t), 65.3 (s), 77.4 (s).
MS (EI) m/z: 162 (M+, 83%), 147 (8%), 133 (11%), 119
(27%), 105 (81%), 91 (100%). IR (cmꢀ1): 2233 (C„C).
1-(p-Anisyl)cyclopentene (5c); (tR = 1.35 min), 137
mg (69%). Colorless needles (m.p. 43–44 °C, from etha-
nol). 1H NMR (d ppm): 1.99 (2H, m), 2.44 (2H, m), 2.52
(2H, m), 3.79 (3H, s), 6.09 (1H, m), 6.82 (2H, d, Jp-anisyl
= 8.71 Hz), 7.37 (2H, d, Jp-anisyl = 8.71 Hz). 13C NMR (d
ppm): 23.3 (t), 33.3 (t), 36.5 (t), 55.2 (q), 85.4 (s), 90.3 (s),
113.9 (d), 115.7 (s), 124.7 (s), 132.8 (d), 137.2 (d), 159.3
(s). MS (EI) m/z: 198 (M+, 100%), 183 (14%), 167 (25%),
155 (36%). IR (cmꢀ1): 2194 (C„C), 1664 (C@C). 1,4-
Di(p-anisyl)-1,3-butadiyne (6c); (tR = 11.47 min), 28
mg (21%). Colorless needles (m.p. 144–145 °C, from eth-
anol). 1H NMR (d ppm): 3.81 (6H, s), 6.85 (4H, d,
J = 8.71 Hz), 7.45 (4H, d, J = 8.71 Hz). 13C NMR (d
ppm); 55.3 (q), 72.9 (s), 81.2 (s), 113.9 (s), 114.1 (d),
134.0 (d), 160.2 (s). MS (EI) m/z: 262 (M+, 100%), 247
(45%), 232 (3%), 219 (8%), 204 (5%), 131 (8%). IR
(cmꢀ1): 2139 (C„C).
4.3.8. Reaction of 3 3-dimethyl-1-butynyldiphenylstibane
(1f) with 1-iodocyclopentene (2)
1-(3,3-Dimethyl-1-butynyl)cyclopentene (5f); (tR =
1
0.933 min), 111 mg (75%). Colorless oil. H NMR (d
ppm): 1.23 (9H, s), 1.52 (2H, m), 1.86 (2H, m), 2.37
(2H, m), 5.80 (1H, m). 13C NMR (d ppm): 23.2 (t),
27.7 (s), 30.5 (q), 32.9 (t), 36.6 (t), 76.0 (s), 99.1 (s),
125.0 (s), 135.3 (d). MS (EI) m/z: 148 (M+, 71%), 133
(100%), 119 (32%), 105 (61%), 91 (32%). IR (cmꢀ1):
2144 (C„C), 1677 (C@C). 2,2,7,7-Tetramethyl-3,5-
octadiyne (6f); (tR = 0.392 min), 10.3 mg (13%). Color-
1
less plates (m.p. 105–110 °C, subl., from ethanol). H
NMR (d ppm): 1.23 (18H, s). 13C NMR (d ppm): 27.9
(s), 30.6 (q), 63.7 (s), 86.2 (s). MS (EI) m/z: 162 (M+,
100%), 147 (55%), 132 (18%), 119 (71%), 105 (59%),
91 (49%). IR (cmꢀ1): 2184 (C„C).
4.3.6. Reaction of p-fluorophenylethynyldiphenylstibane
(1d) with 1-iodocyclopentene (2)
1-(p-Fluorophenylethynyl)cyclopentene (5d); (tR =
2.27 min), 158 mg (85%). Colorless prisms (m.p. 51–53
°C, from ethanol). H NMR (d ppm): 1.94 (2H, m),
2.45–2.49 (2H, m), 2.52–2.55 (2H, m), 6.13 (1H, m),
4.3.9. Reaction of trimethylsilylethynyldiphenylstibane
(1g) with 1-iodocyclopentene (2)
1-(2-Trimethylsilylethynyl)cyclopentene (5g); (tR =
1
1
0
0
0
6.99 (2H, dd, J2 ,3 = J3 ,F = 8.71 Hz), 7.41 (2H, dd,
0
0.542 min), 105 mg (64%). Colorless oil. H NMR (d
J2 ,3 = 8.71 Hz, J2 ,F = 5.50 Hz). 13C NMR (d ppm):
23.3 (t), 33.4 (t), 36.4 (t), 86.4 (s), 89.3 (s), 115.5 (dd,
ppm): 0.14 (9H, s), 1.85 (2H, m), 2.34–2.42 (4H, m),
6.05 (1H, m). 13C NMR (d ppm): 0.21 (q), 23.3 (t),
33.2 (t), 36.3 (t), 95.2 (s), 102.5 (s), 124.6 (s), 139.2 (d).
MS (EI) m/z: 164 (M+, 33%), 149 (100%), 133 (4%),
121 (3%). IR (cmꢀ1): 2148 (C„C), 1648 (C@C). 1,4-
Bis(trimethylsilyl)-1,3-butadiyne (6g); (tR = 0.425 min),
15 mg (15%). Colorless plates (m.p. 112–113 °C subl.,
0
0
2JF = 22.0 Hz), 119.7 (d, JF = 3.9 Hz), 124.4 (s), 133.3
4
3
1
(dd, JF = 8.6 Hz), 138.2 (d), 162.3 (d, JF = 247.1 Hz).
MS (EI) m/z: 186 (M+, 100%), 171 (28%), 165 (57%),
157 (18%), 144 (10%), 133 (13%). IR (cmꢀ1): 2204
(C„C), 1656 (C@C). 1,4-Bis(p-fluorophenyl)-1,3-but-
adiyne (6d); (tR = 4.46 min), 10 mg (8%). Colorless
1
from ethanol). H NMR (d ppm): 0.189 (18H, s). 13C
1
plates (m.p. 195–197 °C, from ethanol). H NMR (d
ppm): 7.04 (4H, dd, J2,3 = J3,F = 8.71 Hz), 7.51 (4H,
NMR (d ppm): ꢀ0.5 (q), 85.9 (s), 88.0 (s). MS (EI) m/
z: 194 (M+, 20%), 179 (100%), 163 (2%), 149 (2%), 135
(2%), 121 (4%). IR (cmꢀ1): 2067 (C„C).
dd, J2,3 = 8.71 Hz, J2,F = 5.50 Hz). 13C NMR (d ppm):
2
73.6 (s), 80.4 (s), 115.9 (dd, JF = 21.9 Hz), 117.8 (s),
134.5 (dd, 3JF = 8.50 Hz), 163.1 (d, 1JF = 249.9 Hz).
MS (EI) m/z: 238 (M+, 100%), 218 (12%), 119 (15%).
IR (cmꢀ1): 2144 (C„C).
4.3.10. Reaction of diphenylphenylethynylstibane (1a)
with 1-iodocyclohexene (7) [19]
1-Phenylethynylcyclohexene (10); (tR = 1.90 min),
121.1 mg (67%). Colorless oil. 1H NMR (d ppm):
1.51–1.69 (4H, m), 2.13–2.22 (4H, m), 6.20 (1H, m),
7.23–7.33 (3H, m), 7.40–7.51 (2H, m). 13C NMR (d
ppm): 21.5 (t), 22.3 (t), 25.7 (t), 29.2 (t), 86.8 (s), 91.2
(s), 120.7 (s), 123.7 (s), 127.6 (d), 128.2 (d), 131.4 (d),
135.1 (d). MS (EI) m/z: 182 (M+, 100%), 167 (62%),
154 (55%), 141 (22%), 126 (20%), 115 (31%). IR
(cmꢀ1): 2202 (C„C), 1592 (C@C). 6a; 30 mg (30%).
4.3.7. Reaction of 1-hexynyldiphenylstibane (1e) with
1-iodocyclopentene (2)
1-(1-Hexynyl)cyclopentene (5e); (tR = 0.54 min), 104
1
mg (70%). Colorless oil. H NMR (d ppm): 0.92 (3H,
t, J = 7.33 Hz), 1.43 (2H, tq, J = 7.33 Hz), 1.50 (2H,
tt, J = 7.33 Hz), 1.88 (2H, m), 2.32 (2H, t, J = 7.33
Hz), 2.39–2.43 (4H, m). 13C NMR (d ppm): 13.6 (q),

2964
N. Kakusawa et al. / Journal of Organometallic Chemistry 690 (2005) 2956–2966
4.3.11. Reaction of diphenylphenylethynylstibane (1a)
with trans-1-iodohexene (8) [22]
trans-1-Phenyl-3-octene-1-yne (11); (tR = 1.49 min),
1H NMR (d ppm): 3.80 (3H, s), 6.86 (2H, d, J = 8.71
Hz), 7.31–7.43 (3H, m), 7.46 (2H, d, J = 8.71 Hz),
7.49–7.52 (2H, m). 13C NMR (d ppm): 55.2 (q), 88.0
(s), 89.4 (s), 114.0 (d), 115.4 (s), 123.6 (s), 127.9 (d),
128.3 (d), 131.4 (d), 133.0 (d), 159.6 (s). MS (EI) m/z:
208 (M+, 100%), 193 (60%), 176 (4%), 165 (40%). IR
(cmꢀ1): 2214 (C„C). 6a; 25 mg (25%).
1
75.2 mg (41%). Colorless oil. H NMR (d ppm): 0.91
(3H, t, J7,8 = 7.33 Hz), 1.32–1.43 (4H, m), 2.16 (2H,
dt, J5,6 = J4,5 = 7.33 Hz), 5.69 (1H, d, J3,4 = 16.04 Hz),
6.24 (1H, dt, J3,4 = 16.04 Hz, J4,5 = 7.33 Hz), 7.24–7.30
(3H, m), 7.40–7.42 (2H, m). 13C NMR (d ppm): 13.8
(q), 22.2 (t), 30.9 (t), 32.9 (t), 87.8 (s), 88.3 (s), 109.5
(d), 123.7 (s), 127.8 (d), 128.2 (d), 131.4 (d), 145.2 (d).
MS (EI) m/z: 184 (M+, 100%), 169 (10%), 155 (55%),
141 (82%), 128 (78%), 115 (68%). IR (cmꢀ1): 2202
(C„C), 1596 (C@C). 6a; 39.4 mg (39%).
4.4.3. Reaction of diphenylphenylethynylstibane (1a) with
o-iodotoluene (13c)
Phenyl(o-tolyl)acetylene (14c); (tR = 4.00 min), 57.6
1
mg (30%). Colorless oil. H NMR (d ppm): 2.54 (3H,
0
s), 7.18 (1H, dd, J5 ,6 = 7.79 Hz, J4 ,5 = 4.58 Hz),
0
0
0
7.24–7.25 (2H, m), 7.34–7.38 (3H, m), 7.52 (1H, d,
J5 ,6 = 7.79 Hz), 7.55–7.56 (2H, m). 13C NMR (d
ppm): 20.7 (q), 88.3 (s), 93.3 (s), 123.0 (s), 123.5 (s),
125.6 (d), 128.1 (d), 128.28 (d), 128.33 (d), 129.4 (d),
131.5 (d), 131.8 (d), 140.2 (s). MS (EI) m/z: 192 (M+,
100%), 165 (25%), 139 (5%), 115 (11%). IR (cmꢀ1):
2215 (C„C). 6a; 20.2 mg (20%).
0
0
4.3.12. Reaction of diphenylphenylethynylstibane (1a)
with trans-b-iodostyrene (9) [23]
trans-1,4-Diphenyl-1-butene-3-yne (12); (tR = 4.88
min), 126.3 mg (62%). Colorless needles (m.p. 99–100
°C, from ethanol). 1H NMR (d ppm): 6.38 (1H, d,
J1,2 = 16.5 Hz), 7.04 (1H, d, J1,2 = 16.5 Hz), 7.25–7.34
(6H, m), 7.39–7.42 (2H, m), 7.46–7.48 (2H, m). 13C
NMR (d ppm): 88.9 (s), 91.8 (s), 108.1 (d), 123.4 (d),
126.3 (d), 128.2 (d), 128.3 (d), 128.6 (d), 128.7 (d),
131.5 (d), 136.3 (s), 141.2 (d). MS (EI) m/z : 204 (M+,
100%), 189 (4%), 176 (5%), 163 (3%), 150 (3%). IR
(cmꢀ1): 2192 (C„C), 1592 (C@C). 6a; 30.5 mg (30%).
4.4.4. Reaction of diphenylphenylethynylstibane (1a) with
p-iodotoluene (13d)
Phenyl(p-tolyl)acetylene (14d); (tR = 4.58 min), 65.3
mg (34%). Colorless prisms (m.p. 69–71 °C, from etha-
nol). 1H NMR (d ppm): 2.35 (3H, s), 7.14 (2H, d,
J = 7.79 Hz), 7.30–7.34 (3H, m), 7.42 (2H, d, J = 7.79
Hz), 7.50–7.52 (2H, m). 13C NMR (d ppm): 21.5 (q),
88.7 (s), 89.6 (s), 120.2 (s), 123.5 (s), 128.0 (d), 128.3
(d), 129.1 (d), 131.475 (d), 131.529 (d), 138.3 (s). MS
(EI) m/z: 192 (M+, 100%), 177 (5%), 165 (12%), 139
(5%), 115 (4%). IR (cmꢀ1): 2216 (C„C). 6a; 20.2 mg
(20%).
4.4. Reaction of diphenylphenylethynylstibane (1a) with
aryl iodides (13a–i)
General procedure. A mixture of diphenylphenylethy-
nylstibane (1a, 376 mg, 1.00 mol) and aryl iodides
(13a–i, 1.50 mmol) and dichloro(bistriphenylphos-
phine)palladium (70.0 mg, 0.10 mmol) in diethylamine
(5 ml) was heated at 55 °C for 24 h under nitrogen atmo-
sphere. After removal of the solvent under reduced pres-
sure, the crude residue was purified on silica gel column
chromatography using a mixture of n-hexane and benzene
to afforded cross-coupling products (14a–i) and 1,4-diph-
enylbutadiyne (6a). Yields of the products were analyzed
by GLC (5% SE30, 1.6 M, column temperature 210 °C)
based on biphenyl (tR = 1.17 min) as an internal standard.
4.4.5. Reaction of diphenylphenylethynylstibane (1a) with
4-fluoro-1-iodobenzene (13e)
p-Fluorophenylphenylacetylene (14e); (tR = 2.96
min), 84.4 mg (43%). Colorless prisms (m.p. 113–114
°C, from ethanol). 1H NMR (d ppm): 7.03 (2H, dd,
0
0
0
J2 ,3 = J3 ,F = 8.70 Hz), 7.32–7.35 (3H, m), 7.49–7.52
(4H, m). 13C NMR (d ppm): 88.3 (s), 89.0 (s), 115.6
(dd, 2JF = 22.0 Hz), 119.4 (s), 123.1 (s), 128.3 (d),
128.4 (d), 131.5 (d), 133.5 (dd, 3JF = 8.63 Hz), 162.5
1
4.4.1. Reaction of diphenylphenylethynylstibane (1a) with
iodobenzene (13a)
(d, JF = 245 Hz). MS (EI) m/z: 196 (M+, 100%), 170
(8%), 144 (4%). IR (cmꢀ1): 2222 (C„C). 6a; 7 mg (7%).
1,2-Diphenylacetylene (14a); (tR = 3.01 min), 81 mg
(46%). Colorless prisms (m.p. 59–61 °C, from ethanol).
1H NMR (d ppm): 7.33–7.38 (6H, m), 7.53–7.57 (4H,
m). 13C NMR (d ppm): 89.4 (s), 96.1 (s), 123.3 (s), 128.2
(d), 128.3 (d), 131.6 (d). MS (EI) m/z: 178 (M+, 100%),
152 (27%), 126 (7%). 6a; (tR = 10.55 min), 21.4 mg (21%).
4.4.6. Reaction of diphenylphenylethynylstibane (1a) with
p-iodoacetophenone (13f)
p-Acetylphenylphenylacetylene (14f); (tR = 12.04
min), 101 mg (46%). Colorless needles (m.p. 99–100
°C, from ethanol). 1H NMR (d ppm): 2.60 (3H, s),
7.36–7.37 (3H, m), 7.54–7.56 (2H, m), 7.60 (2H, d,
J = 8.25 Hz), 7.93 (2H, d, J = 8.25 Hz). 13C NMR (d
ppm): 26.6 (q), 88.6 (s), 92.7 (s), 122.6 (s), 128.1 (s),
128.2 (d), 128.4 (d), 128.8 (d), 131.6 (d), 131.7 (d),
136.1 (s), 197.2 (s). MS (EI) m/z: 220 (M+, 92%), 205
4.4.2. Reaction of diphenylphenylethynylstibane (1a) with
p-iodoanisole (13b)
p-Anisylphenylacetylene (14b); (tR = 8.17 min), 73 mg
(35%). Colorless prisms (m.p. 59–60 °C, from ethanol).

N. Kakusawa et al. / Journal of Organometallic Chemistry 690 (2005) 2956–2966
2965
(100%), 189 (4%), 176 (45%), 151 (15%). IR (cmꢀ1): 2218
(C„C), 1680 (C@O). 6a; 7.1 mg (7%).
Synthesis, Wiley-VCH, Verlag GmbH & Co. KGaA, Weinheim,
2004;
K.-y. Akiba (Ed.), Chemistry of hypervalent compounds, Wiley-
VCH, New York, 1999;
4.4.7. Reaction of diphenylphenylethynylstibane (1a) with
o-iodonitrobenzene (13g)
o-Nitrophenylphenylacetylene (14g); (tR = 11.05
T. Kauffmann, Angew. Chem., Int. Ed. Engl. 21 (1982) 410.
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min), 171 mg (77%). Orange plates (m.p. 192–194 °C,
1
from ethanol). H NMR (d ppm): 7.46–7.55 (4H, m),
7.63 (1H, d, J = 6.88 Hz), 7.67–7.69 (2H, m), 8.63–8.65
(2H, m). 13C NMR (d ppm): 114.2 (d), 121.6 (d), 122.8
(s), 125.8 (s), 127.8 (d), 128.5 (d), 130.7 (d), 131.1 (d),
132.1 (s), 134.8 (d), 147.8 (s), 186.9 (s). MS (EI) m/z:
223 (M+, 100%), 206 (59%), 195 (7%), 179 (12%), 167
(20%). 6a; 11.1 mg (11%).
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Int. Ed. Engl. 40 (2001) 4544.
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m-iodonitrobenzene (13h)
m-Nitrophenylphenylacetylene (14h); (tR = 13.01
(b) D.V. Moiseev, A.V. Gushchin, A.S. Shavirin, Y.A. Kursky,
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1
from ethanol). H NMR (d ppm): 7.37–7.39 (3H, m),
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(2000) 38;
0
7.52 (1H, dd, J4 ,5 = J5 ,6 = 7.79 Hz), 7.54–7.56 (2H,
0
0
0
0
0
0
0
m), 7.81 (1H, d, J5 ,6 = 7.79 Hz), 8.17 (1H, d, J4 ,5 =
(e) S.-K. Kang, H.-C. Ryu, Y.-T. Hong, J. Chem. Soc., Perkin
Trans. 1 (2000) 3350;
7.79 Hz), 8.36 (1H, s). 13C NMR (d ppm): 86.8 (s),
91.9 (s), 122.2 (s), 122.8 (d), 125.1 (s), 126.3 (d), 128.5
(d), 129.0 (d), 129.3 (d), 131.7 (d), 137.2 (d), 148.1 (s).
MS (EI) m/z: 223 (M+, 100%), 176 (43%), 165 (6%),
151 (16%),. IR (cmꢀ1): 2210 (C@C). 6a; 20.2 mg (20%).
(f) M. Fujiwara, M. Tanaka, A. Baba, H. Ando, Y. Souma, J.
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p-Nitrophenylphenylacetylene (14i); (tR = 12.64 min),
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Jpn. 69 (1996) 2341;
194 mg (87%). Colorless needles (m.p. 121–123 °C, from
1
ethanol). H NMR (d ppm): 7.37–7.40 (3H, m), 7.55–
(c) L.-J. Zhang, Y.-Z. Huang, J. Organomet. Chem. 454 (1993)
101;
7.57 (2H, m), 7.66 (2H, J = 8.71 Hz), 8.21 (2H, d,
J = 8.71 Hz). 13C NMR (d ppm): 87.5 (s), 94.7 (s),
122.1 (s), 123.6 (d), 128.55 (d), 129.2 (d), 130.2 (s),
131.8 (d), 132.2 (d), 146.9 (s). MS (EI) m/z: 223 (M+,
100%), 207 (2%), 193 (30%), 176 (72%), 165 (24%),
151 (26%). IR (cmꢀ1): 2215 (C„C). 6a; 5.1 mg (5%).
(d) Y.-Z. Huang, Acc. Chem. Res. 25 (1992) 182.
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(d) A.L. Casado, P. Espinet, A.M. Gallego, J. Am. Chem. Soc.
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Acknowledgments
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This research was supported by a Grant-in-Aid for
Scientific Research on Priority Areas (A) ÔExploitation
of Multi-Element Cyclic MoleculesÕ from The Ministry
of Education, Culture, Sports, Science and Technology
(MEXT), Japan. Financial support by The Specific Re-
search Fund of Hokuriku University was also gratefully
acknowledged.
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compounds: C.G. Bates, P. Saejueng, D. Venkataraman, Org.
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