One-Pot Domino Synthesis of Diarylalkynes/1,4-Diaryl-1,3-diynes by [9,9-Dimethyl-4,5-bis(diphenylphosphino)xanthene] (Xantphos)–Copper(I) Iodide–Palladium(II) Acetate-Catalyzed Double Sonogashira-Type Reaction

Article abstract of DOI:10.1002/adsc.201701128

The low loading combination of the complex [9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene] (Xantphos)copper(I) iodide and simple ligand-free palladium(II) acetate was found to be efficient for the domino synthesis of diarylalkynes by the reaction of aryl halides with trimethylsilylethynylene or bis(trimethylsilyl)acetylene in a single-step procedure. The unsymmetrical diarylalkynes can be obtained through a one-pot two-step approach. The reactions of aryl bromides with 1,4-bis(trimethylsilyl)butadiyne also furnished the corresponding 1,4-diaryl-1,3-diynes in a similar fashion. This route to diarylalkynes and 1,4-diaryl-1,3-diynes is complementary to previously reported synthetic procedures. (Figure presented.).

Full text of DOI:10.1002/adsc.201701128

Title: One-pot Domino Synthesis of Diarylalkynes/1,4-Diaryl-1,3-diynes
by [9,9-Dimethyl-4,5-bis(diphenylphosphino)xanthene]Copper(I)
Iodine–Palladium(II) Acetate Catalyzed Double Sonogashira-type
Reaction
Authors: Shaozhong Qiu, Caiyang Zhang, Rui Qiu, Guodong Yin, and
Jinkun Huang
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201701128
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10.1002/adsc.201701128
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
One-pot Domino Synthesis of Diarylalkynes/1,4-Diaryl-1,3-
diynes by [9,9-Dimethyl-4,5-bis(diphenylphosphino)xanthene]-
Copper(I) Iodine–Palladium(II) Acetate Catalyzed Double
Sonogashira-type Reaction
Shaozhong Qiu,a Caiyang Zhang,a Rui Qiu,a Guodong Yina,* and Jinkun Huangb,*
a Hubei Collaborative Innovation Center for Rare Metal Chemistry, Hubei Key Laboratory of Pollutant Analysis and
Reuse Technology, Hubei Normal University, Huangshi 435002, People's Republic of China
Tel: (+86)-714-6515602; E-mail: gdyin@hbnu.edu.cn
b Xiling Lab, Chengdu 610041, People's Republic of China
E-mail: jinkunh@xilinglab.com
Received: ((will be filled in by the editorial staff))
This paper is dedicated to Professor Elias J. Corey on the occasion of his 90th birthday.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######. ((Please
delete if not appropriate))
Abstract. The low loading combination of complex [9,9- with 1,4-bis(trimethylsilyl)butadiyne also furnished the
dimethyl-4,5-bis(diphenylphosphino)xanthene]copper(I)
corresponding 1,4-diaryl-1,3-diynes in a similar fashion.
iodide and simple ligand-free palladium(II) acetate was This route to diarylalkynes and 1,4-diaryl-1,3-diynes is
found efficient for the domino synthesis of diarylalkynes by complementary to previously reported synthetic procedures.
the reaction of aryl halides with trimethylsilylethynylene or
bis(trimethylsilyl)acetylene in a single-step procedure. The
unsymmetrical diarylalkynes can be obtained through a one-
pot two-step approach. The reactions of aryl bromides
Keywords: diarylalkynes; alkynylation; domino reactions;
Sonogashira-type coupling; one-pot synthesis
bis(trimethylsilyl)acetylene.[14]
Among
them,
Introduction
trimethylsilylacetylene is the most frequently used
acetylene synthon for the domino synthesis of
diarylalkynes due to its availability as well as mild
deprotection conditions.[15] The pioneering work of
this domino reaction is reported by Brisbios and co-
workers through in situ deprotection of
Diarylalkynes are very important precursors in
organic synthesis,[1] which can be converted into a
variety of functionalized molecules, including
biologically active heterocycles via click chemistry[2]
and organic materials.[3] The palladium-catalyzed
coupling of aryl halides with diborylethyne[4] via
trimethylsilylethynylene-added
intermediates.[16]
However, aryl iodides appear more efficient for this
reaction, though 4-CN, 4-NMe2 and phenyl-
substituted bromobenzenes are reported inactive even
Suzuki-Miyaura
reaction
or
with
bis(tributylstannyl)acetylene[5] via Stille reaction is
practicably useful under certain circumstancese.
Nevertheless, these reactions are often limited by the
availability of acetylene resources. In general,
Sonogashira-type coupling of aryl halides with
terminal arylacetylenes is a more powerful strategy.[6]
o
at 80 C. Apparently, most of these existing one-pot
methods have some drawbacks including the
limitation in aryl halide substrates, low yield, high
reaction temperature or high catalyst loading.
Accordingly, a more efficient one-pot approach to
symmetrical or unsymmetrical diarylalkynes is still
highly desired. Recently, Huang et al. first prepared
the Cu(Xantphos)I complex by the simple mixing of
9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene
(Xantphos) with copper(I) iodide in acetonitrile and
found it can effectively catalyze the C–C/C≡C
bonding formation in the presence of a palladium
source.[17] In a continuation of our efforts to use this
copper complex in organic synthesis, herein we
In
order
to
avoid
the
multi-step
protection/deprotection approach to terminal
arylacetylenes,[7] the direct reaction of aryl halides
with various acetylene synthons in a one-pot domino
procedure has been developed in recent years
(Scheme 1). The acetylene synthons include gaseous
acetylene,[8] lithium acetylide,[9] 2-methylbut-3-yn-2-
ol,[10] propiolic acid,[11] 2-butynedioic acid,[12]
trimethylsilylacetylene[13]
and
1
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10.1002/adsc.201701128
Advanced Synthesis & Catalysis
1
2
3
4
5
6
7
1.0/1.0 Cu(Xantphos)I
1.0/0.5 Cu(Xantphos)I
1.0/0.6 Cu(Xantphos)I
1.0/0.7 Cu(Xantphos)I
1.0/0.8 Cu(Xantphos)I
DMF
DMF
DMF
DMF
DMF
57/0
84/0
would like to report the Pd(OAc)2/Cu(Xantphos)I
system for efficient synthesis of diarylalkynes in a
one-pot domino procedure from aryl halides and
93(83[d])/0
74/0
trimethylsilylethynylene
or
68/0
0/81
bis(trimethylsilyl)acetylene.
1.0/0.5 Cu(Xantphos)I Toluene
1.0/1.2 Cu(Xantphos)I Toluene 0/77(0/82[e])
8
9
10
1.0/0.6 CuI
DMF
DMF
DMF
trace/0
61/0
<10/0
1.0/0.6 CuI[f]
1.0/0.6 Cu(PPh3)3I
[a] All of the reactions were carried out with 1a (1.0 mmol),
2a (0.5–1.2 mmol), Pd(OAc)2 (0.01 mmol) and [Cu] (0.01
mmol) and Cs2CO3 (2.0 mmol) in anhydrous DMF (3 mL)
at 60 oC for 24 h unless otherwise specified.
[b] Xantphos = 9,9-Dimethyl-4,5-bis(diphenylphosphino)-
xanthene.
[c] Yield was determined by GC based on the amount of 1a.
[d] Isolated yield.
Scheme 1. Synthesis of diarylalkynes from various
acetylene synthons
[e] Iodobenzene was used at room temperature for 12 h.
[f] Pd(Xantphos)2 (0.01 mmol) was employed.
Results and Discussion
With the optimized conditions in hand, we
examined the reaction scope using a variety of aryl
halides, and the results are summarized in Table 2. It
was found that the reactions displayed good
functional group tolerance. Substrates bearing
electron-rich (-Me, -OMe, -SMe, -NMe2) and
electron-deficient (-NO2, -COMe, -CN, -CF3, -
SO2Me) substitutents on the phenyl ring could be
converted to the corresponding symmetrical
diarylalkynes 3b−3j in moderate to good yields. The
structure of 3j was confirmed by X-ray
crystallographic analysis (Figure 1). The reactions
proceeded smoothly at room temperature using aryl
iodides as the substrates, affording the corresponding
product 3a, 3c and 3f in 77−86% yields. This
transformation was also suitable for naphthalene ring
(3k). The heterocyclic substrates such as pyridine,
quinoline, isoquinoline, furan, thiophene, and
benzo[b]thiophene also furnished 3l−3t in 71−83%
yields. Apparently, the substitution position of
bromine atom on these heterocycles did not
significantly affect the reaction yields. 1,2-Di(thiazol-
2-yl)ethyne (3u) can be used as an attractive synthon
for the preparation of supramolecular ligand, and it
was obtained in less than 32% yield from 2-
bromothiazole and trimethylsilyl acetylene in three
steps protection/deprotection sequence.[19] To our
delight, by using our one-pot procedure, a better yield
of 3u was afforded. Similarly, the new fascinating
molecule 1,2-di(pyrimidin-2-yl)ethyne 3v was also
obtained in 71% yield. The X-ray crystallographic
analysis indicates all the atoms in this struture are
nearly in a plane (Figure 2). Next, (E)-(2-
bromovinyl)benzene and (2-bromoethene-1,1,2-
triyl)tribenzene were also suitable for this
Following the previous experimental results
conditions,[17b] we investigated the coupling reaction
between bromobenzene (1.0 mmol, 1a) and
trimethylsilylacetylene (1.0 mmol, 2a) in the
presence of Pd(OAc)2 (1 mol%) and Cu(Xantphos)I
(1 mol%) using Cs2CO3 as base in anhydrous DMF at
o
60 C for 24 h, and it was found that the expected
product trimethyl(phenylethynyl)silane (3a’) was not
observed. Instead, the reaction afforded the
symmetrical 1,2-diphenylethyne (3a) in 57% yield
with the recovery of unreacted bromobenzene (Table
1, entry 1). The amount of 2a was reduced to 0.5
equiv, resulting in an obvious improvement of yield
to 84%. Best result (93%) was obtained with 1:0.6
ratio of 1a/2a (Table 1, entries 2–5). Notably, the
mono-Sonogashira coupling product 3a’ was the
major product when the less polar toluene was used
as solvent, and 3a was surprisingly not observed
(Table 1, entries 6, 7). In the meantime, 3a’ was
afforded in good yield at room temperature by
replacing bromobenzene with iodobenzene (Table 1,
entry 7). Trace amount of expected product was
observed instead of CuI and Cu(PPh3)3I with
Cu(Xantphos)I (Table 1, entries 8, 10). In addition,
[18]
the combination of Pd(Xantphos)2 with CuI gave
3a in 61% yield (Table 1, entry 9).
Table 1. Optimization of reaction conditions for the
synthesis of 1,2-diphenylethyne[a]
transformation, delivering the
corresponding
dienynes 3w and 3x in 75% and 68% yields,
respectively.
Yield[c](%)
3a/3a’
Entry
[Cu][b]
Solvent
1a/2a
2
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10.1002/adsc.201701128
Advanced Synthesis & Catalysis
It has been reported that the trimethylsilyl
group can be easily removed in the presence of
inorganic
trimethyl(phenylethynyl)silane
base.[20]
We
also
found
(3a’)
that
gave
phenylacetylene in nearly quantitative yield in the
presence of Cs2CO3 in DMF within 10 min. Notably,
Nishihara and co-workers reported that under non-
basic conditions, the sila-Sonogashira coupling
reaction of aryl iodides with alkynylsilanes proceeded
soomthly via the Si-C bond direct activation by using
Figure 1. X-ray structures of compounds 3j (CCDC No.
1570103)
14c, 21]
the Pd/Cu co-catalyst system in DMF.[13a,
Accordingly, bis(trimethylsilyl)acetylene (2b) was
employed to react with several representative aryl
bromines, also resulting in the diarylalkynes 3a−3c,
3f and 3i in 71−80% yields (Scheme 2).
Figure 2. X-ray structures of compounds 3v (CCDC No.
1570104)
Table 2. One-pot domino synthesis of diarylalkynes and diaryldienynes from aryl bromides or iodides and
trimethylsilylacetylene[a, b]
[a] All of the reactions were carried out with 1 (1.0 mmol), 2a (0.6 mmol), Pd(OAc)2 (0.01 mmol) and Cu(Xantphos)I (0.01
mmol) and Cs2CO3 (2.0 mmol) in anhydrous DMF (3 mL) at 60 oC for 24 h unless otherwise specified.
[b] Isolated yields based on the amount of aryl halides (1).
[c] Aryl iodides were employed at room temperature for 12 h.
[d] 0.8 mmol of 2a was employed.
[e] Pd(OAc)2 (0.02 mmol) and Cu(Xantphos)I (0.02 mmol) were employed.
3
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10.1002/adsc.201701128
Advanced Synthesis & Catalysis
Scheme 2. One-step domino synthesis of diarylalkynes from aryl bromides and bis(trimethylsilyl)acetylene
Scheme 3. Competing coupling of aryl bromides with trimethylsilylacetylene
In order to investigate the relative reaction
activity, the competing coupling of two different aryl
bromines with 2a was examined (Scheme 3). Two
added to the above mixture at 60 oC. The
experimental results showed that the corresponding
cross-coupling products 3ae, 3af and 3av were
obtained in good yields, and the symmetrical
products were not observed. In addition, the step-wise
reaction of 1-bromo-4-methoxybenzene, 2a and (E)-
(2-bromovinyl)benzene also gave the eneyne 3cw in
58% yield (Scheme 4).
1,3-Diynes are also ubiquitous structural motifs
in functional materials and important intermediates in
organic synthesis.[22] The copper-catalyzed Glaser
oxidative homo-coupling of terminal alkynes is the
widely used method.[23] In recent years, some
attractive approaches to 1,3-diynes have been
developed.[24] Several examples between the reactions
of aryl iodides with 1,4-bis(trimethylsilyl)butadiyne
(2c) gave the corresponding 1,4-diaryl-1,3-diynes.[25]
Herein, we also expected to obtain the symmetrical
1,3-diynes directly from the reaction of the more
easily available aryl bromides with 2c in one-pot. We
were pleased to find that the desired products 4a−4e
were isolated in 52−64% yields, as shown in Scheme
5.
electron-rich
(-Me
and
-OMe)
substituted
bromobenzenes gave a mixture of homo-coupling
products 3b/3c and cross-coupling product 3bc.
When the competing coupling occurred between
electron-rich (-OMe) and electron-deficient (-CF3)
substituted bromobenzenes, the reaction gave the
homo-coupling 3i as the major product while small
amount of 3c/3ci was observed with the recovery of
unreacted starting material 1b. This may be attributed
to the higher reaction activity for the electron-
deficient substrate.
Ideally, it is our desire to effectively obtain the
unsymmetrical diarylalkynes in a one-pot procedure
by using the present catalytic system. It was observed
that in the less polar solvent toluene, the resulting
trimethylsilyl group was stable (Table 1, entries 6, 7).
Accordingly, a one-pot, two-step reaction procedure
was examined. The reaction was carried out with the
first phenyl halides (1) and 2a in toluene at 60 oC (for
X = Br) or room temperature (for X = I), then the
solution of the second aryl bromides in DMF was
4
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10.1002/adsc.201701128
Advanced Synthesis & Catalysis
Scheme 4. One-pot two-step reaction for the synthesis of unsymmetrical diarylalkynes
Scheme 5. One-pot reaction for the synthesis of symmetrical diaryl-1,3-diynes
Jean-Cyrille Hierso[26] and Manoj Trivedi[27]
In
conclusion,
we
found
that
the
independently found that the low loading of
Pd(OAc)2/Cu(Xantphos)I system is effective for the
domino synthesis of diarylalkynes from aryl halides
[Pd(allyl)Cl]2/copper(I)
tetraphosphine complexes and [Pd(allyl)Cl]2/[Cu4(μ2-
I)2(μ3-I)2(μ-dtbpf)2] (dtbpf 1,1′-bis(di-tert-
iodide
ferrocenyl
and
frequently
used
acetylene
as well
synthon
as
=
trimethylsilylethynylene
butylphosphino)ferrocene) were efficient synergetic
system for Sonogashira coupling reaction, which are
representative examples for the phosphine ligand
complexation to copper instead of commonly used
palladium. Moreover, Chin-Fa Lee demonstrated that
in the absence of palladium salt, Cu(Xantphos)I can
activate the terminal acetylenes and catalyze
Sonogashira coupling of aryl/alkenyl iodides and
bromides with terminal alkynes under microwave
irradiation. But high reaction temperature (135 oC) is
required even for aryl iodides. In addition, our
further experimental results showed that in the
presence of Pd(OAc)2, only trace amount of expected
product was observed replacement of Cu(Xantphos)I
with CuI and Cu(PPh3)3I (Table 1, entries 8, 10). The
Pd(Xantphos)2/CuI catalytic system gave 3a in 61%
yield (Table 1, entry 9). Accordingly, the probable
bis(trimethylsilyl)acetylene in a one-pot procedure.
The reactions of aryl bromides with 1,4-
bis(trimethylsilyl)butadiyne also furnished the
corresponding symmetrical 1,4-diaryl-1,3-diynes.
The easy preparation and excellent stability of
Cu(Xantphos)I, low loading of ligand-free palladium
salt Pd(OAc)2, mild reaction conditions, convenient
execution as well as the wide range of substrates
make this new system be competitive in currently
known methods, which is an efficient route to
diarylalkynes and 1,4-diaryl-1,3-diynes.
Experimental Section
General Information: All the chemicals were
commercially available and used without further
purification. All solvents were dried and distilled
1
according to standard procedures. H and 13C NMR
reason for this
mild and
high-efficient
Pd(OAc)2/Cu(Xantphos)I catalytic coupling system
is that Cu(Xantphos)I could more efficiently activate
the terminal acetylenes than copper(I) iodide due to
the effect by Xantphos.
were recorded in CDCl3 using Bruker Avance II 300
MHz spectrometers at 300 and 75 MHz, respectively.
Chemical shifts are reported relative to TMS (internal
standard). High resolution mass spectra were recorded
using a Bruker ultrafleXtreme MALDI-TOF/TOF
(HCCA matrix) or Solanx70 FT-MS or Thermo
Scientific LTQ Orbitrap XL. IR spectra were obtained
as KBr pellet samples using a Nicolet 5700 FTIR
spectrometer. Flash column chromatography was
performed on silica gel (200–300 mesh). Melting points
Conclusion
5
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10.1002/adsc.201701128
Advanced Synthesis & Catalysis
were determined using an uncorrected X-4 apparatus.
The X-ray crystal structure determination was
performed using a Bruker Smart APEX CCD system.
123.8, 92.0; HRMS m/z (ESI) calcd for C14H9N2O4:
269.0557, found: 269.0548 [M+H]+.
1,1'-(Ethyne-1,2-diylbis(4,1-phenylene))diethanone
(3g).[16a] Yellow solid; yield 48%, 63 mg; m.p. 198–
200 °C; 1H NMR (300 MHz, CDCl3) δ 7.96 (d, J = 8.4 Hz,
4H), 7.64 (d, J = 8.4 Hz, 4H), 2.63 (s, 6H); 13C NMR (75
MHz, CDCl3) δ 197.2, 136.6, 131.9, 128.3, 127.5, 91.6,
26.6; HRMS m/z (ESI) calcd for C18H14O2: 262.0988,
found: 262.0982 [M]+.
General procedure for one-pot synthesis of symmetry
diarylalkynes 3a–3x, 4a–4e (Schemes 1, 2, 5)
The mixture of aryl halides (1, 1.0 mmol) and
trimethylsilylethynylene
(2a,
0.6
mmol)
or
bis(trimethylsilyl)acetylene (2b, 0.6 mmol) or 1,4-
bis(trimethylsilyl)butadiyne (2c, 0.6 mmol), Pd(OAc)2
(2.3 mg, 0.01 mmol), Cu(Xantphos)I (7.7 mg, 0.01 mmol)
and Cs2CO3 (652 mg, 2.0 mmol) in anhydrous DMF (3
mL) was heated at 60 oC for 12–24 h under argon
atmosphere. After the reactions were completed, DMF
was removed under reduced pressure. The mixture was
extracted with ethyl acetate (3×15 mL) three times, and
the combined organic layers were dried over anhydrous
Na2SO4 and filtered. After removal of the solvent, the
residue was purified by flash column chromatography on
silica gel using petroleum ether or the mixture of ethyl
acetate/petroleum ether (v:v, 1/100 to 1/2) as the eluent to
afford the target products.
4,4'-(Ethyne-1,2-diyl)dibenzonitrile (3h).[5c] Yellow solid;
yield 40%, 46 mg; m.p. 253–254 °C; 1H NMR (300 MHz,
CDCl3) δ 7.69–7.61 (m, 8H); 13C NMR (75 MHz, CDCl3)
δ 132.3, 132.2, 127.1, 118.2, 112.4, 91.5; HRMS m/z
(ESI) calcd for C16H9N2: 229.0760, found: 229.0758
[M+H]+.
1,2-Bis(4-(trifluoromethyl)phenyl)acetylene (3i).[8a] White
1
solid; yield 76%, 119 mg; m.p. 107–108 °C; H NMR
(300 MHz, CDCl3) δ 7.67–7.61 (m, 8H); 13C NMR (75
MHz, CDCl3) δ 132.5, 130.6 (q, JC-F = 32.6 Hz), 126.9,
126.0 (d, JC-F = 3.6 Hz), 120.7 (d, JC-F = 270.6 Hz), 90.6;
HRMS m/z (ESI) calcd for C16H9F6: 315.0603, found:
315.0600 [M+H]+.
Diphenyl acetylene (3a).[8f] White solid; yield 83%, 74
1
mg; m.p. 60–61 °C; H NMR (300 MHz, CDCl3) δ 7.54–
1,2-Bis(4-(methylsulfonyl)phenyl)ethyne (3j). Yellow
7.50 (m, 4H), 7.32–7.27 (m, 6H); 13C NMR (75 MHz,
CDCl3) δ 131.5, 128.3, 128.2, 123.2, 89.4; HRMS m/z
(ESI) calcd for C14H11: 179.0855, found: 179.0861
[M+H]+.
1
solid; yield 72%, 120 mg; m.p. 292–293 °C; H NMR
(300 MHz, CDCl3) δ 7.97 (d, J = 8.4 Hz, 4H), 7.74 (d, J =
8.4 Hz, 4H), 3.09 (s, 6H); 13C NMR (75 MHz, CDCl3) δ
140.5, 132.6, 128.0, 127.6, 91.1, 44.4; IR (KBr) ν: 770,
843, 967, 1088, 1141, 1304, 1399, 1596, 1631, 2852, 2925,
3432 cm-1; HRMS m/z (ESI) calcd for C16H14O4S2Na:
357.0226, found: 357.0222 [M+Na]+.
Bis(p-tolyl)acetylene (3b).[8f] White solid; yield 85%, 88
mg; m.p. 131–133 °C; 1H NMR (300 MHz, CDCl3) δ 7.41
(d, J = 7.7 Hz, 4H), 7.14 (d, J = 7.7 Hz, 4H), 2.36 (s, 6H);
13C NMR (75 MHz, CDCl3) δ 138.2, 131.4, 129.1, 120.4,
88.9, 21.5; HRMS m/z (ESI) calcd for C16H15: 207.1168,
found: 207.1177 [M+H]+.
1,2-Bis(4-methoxyphenyl)acetylene (3c).[8f] Yellow solid;
yield 84%, 100 mg; m.p. 140–142 °C; 1H NMR (300 MHz,
CDCl3) δ 7.46–7.43 (m, 4H), 6.88–6.84 (m, 4H), 3.80 (s,
6H); 13C NMR (75 MHz, CDCl3) δ 159.3, 132.8, 115.6,
113.9, 87.9, 55.2; HRMS m/z (ESI) calcd for C16H14O2:
238.0988, found: 238.0986 [M]+.
1,2-Bis(2-(methylthio)phenyl)ethyne (3d).[29] Yellow
solid; yield 75%, 101 mg; m.p. 123–124 °C; 1H NMR
(300 MHz, CDCl3) δ 7.54 (dd, J1 = 7.6 Hz, J2 = 1.0 Hz,
2H), 7.33–7.27 (m, 2H), 7.18 (d, J = 7.8 Hz, 2H), 7.14–
7.09 (m, 2H), 2.52 (s, 6H); 13C NMR (75 MHz, CDCl3) δ
141.6, 132.6, 128.8, 124.22, 124.20, 121.3, 93.1, 15.2;
HRMS m/z (ESI) calcd for C16H15S2: 271.0610, found:
271.0614 [M+H]+.
1,2-Di(naphthalen-1-yl)ethyne (3k).[16a] Yellow solid;
yield 82%, 114 mg; m.p. 127–129 °C; 1H NMR (300 MHz,
CDCl3) δ 8.57 (d, J = 8.4 Hz, 2H), 7.91–7.88 (m, 6H),
7.64–7.51 (m, 6H); 13C NMR (75 MHz, CDCl3) δ 133.3,
130.6, 128.9, 128.4, 126.9, 126.5, 126.3, 125.3, 121.1,
92.4; HRMS m/z (ESI) calcd for C22H15: 279.1168, found:
279.1161 [M+H]+.
1,2-Di(pyridine-2-yl)ethyne (3l).[5c] Brown solid; yield
80%, 72 mg; m.p. 71–73 °C; 1H NMR (300 MHz, CDCl3)
δ 8.64 (d, J = 4.8 Hz, 2H), 7.73–7.68 (m, 2H), 7.62 (d, J =
7.8 Hz, 2H), 7.30–7.27 (m, 2H); 13C NMR (75 MHz,
CDCl3) δ 150.1, 142.8, 136.2, 127.7, 123.3, 87.9; HRMS
m/z (ESI) calcd for C12H9N2: 181.0760, found: 181.0759
[M+H]+.
1,2-Bis(5-chloropyridin-2-yl)ethyne (3m). Yellow solid;
yield 78%, 97 mg; m.p. 204–206 °C; 1H NMR (300 MHz,
CDCl3) δ 8.60 (d, J = 2.0 Hz, 2H), 7.70 (dd, J1 = 8.4 Hz,
J2 = 2.5 Hz, 2H), 7.56 (d, J = 8.4 Hz, 2H); 13C NMR (75
MHz, CDCl3) δ 149.3, 140.3, 136.2, 132.2, 128.3, 87.8; IR
(KBr) ν: 744, 834, 1007, 1110, 1400, 1596, 1631, 2851,
2922, 3424, 3726 cm-1; HRMS m/z (MALDI) calcd for
C12H7Cl2N2: 248.9981, found: 248.9971 [M+H]+.
4,4'-(Ethyne-1,2-diyl)bis(N,N-dimethylaniline)
(3e).[30]
1
Yellow solid; yield 73%, 96 mg; m.p. 232–234 °C; H
NMR (300 MHz, CDCl3) δ 7.38 (dd, J1 = 6.9 Hz, J2 = 2.1
Hz, 4H), 6.67–6.64 (m, 4H), 2.97 (s, 12H); 13C NMR (75
MHz, CDCl3) δ 149.7, 132.4, 111.9, 111.1, 88.1, 40.3;
HRMS m/z (ESI) calcd for C18H21N2: 265.1699, found:
265.1699 [M+H]+.
1,2-Di(pyridin-3-yl)ethyne (3n).[5c] White solid; yield 78%,
1
70 mg; m.p. 59–60 °C; H NMR (300 MHz, CDCl3) δ
1,2-Bis(4-nitrophenyl)ethyne (3f).[8f] Yellow solid; yield
8.79 (d, J = 1.3 Hz, 2H), 8.59 (dd, J1 = 4.9 Hz, J2 = 1.6 Hz,
2H), 7.86–7.82 (m, 2H), 7.34–7.30 (m, 2H); 13C NMR (75
MHz, CDCl3) δ 152.2, 149.0, 138.5, 123.1, 119.7, 89.1;
1
72%, 96 mg; m.p. 214–215 °C; H NMR (300 MHz,
CDCl3) δ 8.26 (d, J = 8.9 Hz, 4H), 7.71 (d, J = 8.8 Hz,
4H); 13C NMR (75 MHz, CDCl3) δ 147.7, 132.6, 128.9,
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701128
Advanced Synthesis & Catalysis
HRMS m/z (ESI) calcd for C12H9N2: 181.0760, found:
3432 cm-1; HRMS m/z (MALDI) calcd for C10H7N4:
181.0761 [M+H]+.
183.0665, found: 183.0670 [M+H]+;
1,2-Di(isoquinolin-4-yl)ethyne (3o).[5c] White solid; yield
71%, 99 mg; m.p. 235–236 °C; 1H NMR (300 MHz,
CDCl3) δ 9.27 (s, 2H), 8.91 (s, 2H), 8.43 (d, J = 8.3 Hz,
2H), 8.06 (d, J = 8.2 Hz, 2H), 7.88 (t, J = 7.1 Hz, 2H),
7.72 (t, J = 7.2 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ
152.5, 146.8, 135.4, 131.4, 128.1 (2C), 127.8, 125.0, 115.6,
91.7; HRMS m/z (ESI) calcd for C20H13N2: 281.1073,
found: 281.1075 [M+H]+.
(1E,
5E)-1,6-Diphenylhexa-1,5-dien-3-yne
(3w).[33]
Yellow solid; yield 75%, 86 mg; m.p. 57–59 °C; 1H NMR
(300 MHz, CDCl3) δ 7.43–7.40 (m, 4H), 7.37–7.34 (m,
3H), 7.31–7.28 (m, 3H), 7.01 (s, 1H), 6.96 (s, 1H), 6.37 (s,
1H), 6.32 (s, 1H); 13C NMR (75 MHz, CDCl3) δ 141.1,
136.3, 128.7, 128.6, 126.3, 108.2, 91.5; HRMS m/z (ESI)
calcd for C18H14Na: 253.0988, found: 253.0993 [M+Na]+.
Hexa-1,5-dien-3-yne-1,1,2,5,6,6-hexaylhexabenzene (3x).
Yellow solid; yield 68%, 181 mg; m.p. 244–245 °C; H
1,2-Di(quinolin-3-yl)ethyne (3p).[5c] White solid; yield
1
1
76%, 106 mg; m.p. 169–171 °C; H NMR (300 MHz,
NMR (300 MHz, CDCl3) δ 7.39–7.27 (m, 5H), 7.24–7.19
(m, 5H), 7.09–7.03 (m, 12H), 6.97–6.95 (m, 4H), 6.92–
6.89 (m, 4H); 13C NMR (75 MHz, CDCl3) δ 148.2, 142.6,
141.5, 139.2, 131.1, 130.3, 130.0, 127.8, 127.7, 127.63,
127.57, 127.1, 126.6, 122.0, 95.6; IR (KBr) ν: 708, 773,
1028, 1074, 1350, 1400, 1440, 1486, 1596, 1631, 3432,
3773 cm-1; HRMS m/z (MALDI) calcd for C42H30:
534.2342, found: 534.2345 [M]+.
CDCl3) δ 9.06 (d, J = 2.0 Hz, 2H), 8.39 (d, J = 1.8 Hz, 2H),
8.13 (d, J = 8.5 Hz, 2H), 7.84 (d, J = 8.1 Hz, 2H), 7.79–
7.74 (m, 2H), 7.60 (t, J = 7.4 Hz, 2H); 13C NMR (75 MHz,
CDCl3) δ 151.9, 147.1, 138.7, 130.4, 129.5, 127.7, 127.5,
127.2, 116.8, 89.8; HRMS m/z (ESI) calcd for C20H13N2:
281.1073, found: 281.1082 [M+H]+.
1,2-Di(quinolin-6-yl)ethyne (3q). Yellow solid; yield 73%,
1
102 mg; m.p. 162–163 °C; H NMR (300 MHz, CDCl3) δ
1,4-Diphenylbuta-1,3-diyne (4a).[34] White solid; yield
64%, 65 mg; m.p. 85–86 °C; 1H NMR (300 MHz, CDCl3)
δ 7.55–7.52 (m, 4H), 7.38–7.30 (m, 6H); 13C NMR (75
MHz, CDCl3) δ 132.5, 129.2, 128.4, 121.8, 81.5, 73.9;
HRMS m/z (ESI) calcd for C16H11: 203.0855, found:
203.0865 [M+H]+.
8.94 (dd, J1 = 4.2 Hz, J2 = 1.5 Hz, 2H), 8.18–8.10 (m, 3H),
8.09 (d, J = 1.6 H z, 3H), 7.87 (dd, J1 = 8.7 Hz, J2 =1.8 Hz,
2H), 7.45 (dd, J1 = 8.3 Hz, J2 = 4.3 Hz, 2H); 13C NMR (75
MHz, CDCl3) δ 151.1, 147.8, 135.8, 132.1, 131.3, 129.7,
128.0, 121.8, 121.3, 90.2; IR (KBr) ν: 761, 831, 946,
1115, 1349, 1400, 1589, 1632, 2852, 2923, 3432, 3726
cm-1; HRMS m/z (MALDI) calcd for C20H13N2: 281.1073,
found: 281.1069 [M+H]+.
1,4-Di-p-tolylbuta-1,3-diyne (4b).[34] White solid; yield
61%, 70 mg; m.p. 182–183 °C; 1H NMR (300 MHz,
CDCl3) δ 7.42 (d, J = 8.1 Hz, 4H), 7.14 (d, J = 8.0 Hz, 4H),
2.36 (s, 6H); 13C NMR (75 MHz, CDCl3) δ 139.5, 132.4,
129.2, 118.8, 81.5, 73.4, 21.6; HRMS m/z (ESI) calcd for
C18H14: 230.1096, found: 230.1093 [M]+.
1,2-Di(furan-3-yl)ethyne (3r).[31] Yellow solid; yield 81%,
1
64 mg; m.p. 64–65 °C; H NMR (300 MHz, CDCl3) δ
7.65 (d, J = 0.6 Hz, 2H), 7.39 (t, J = 1.6 Hz, 2H), 6.49 (d,
J = 1.2 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ 145.4,
142.9, 112.4, 107.5, 82.0; HRMS m/z (ESI) calcd for
C10H6O2: 158.0368, found: 158.0377 [M]+.
1,4-Bis(4-methoxyphenyl)buta-1,3-diyne (4c).[34] Yellow
solid; yield 59%, 77 mg; m.p. 139–140 °C; H NMR (300
MHz, CDCl3) δ 7.45 (d, J = 8.7 Hz, 4H), 6.85 (d, J = 8.7
Hz, 4H), 3.82 (s, 6H); 13C NMR (75 MHz, CDCl3) δ 160.3,
134.0, 114.1, 114.0, 81.2, 73.0, 55.3; HRMS m/z (ESI)
calcd for C18H14O2: 262.0988, found: 262.0979 [M]+.
1
1,2-Di(thiophen-2-yl)ethyne (3s).[16a] White solid; yield
83%, 78 mg; m.p. 98–99 °C; 1H NMR (300 MHz, CDCl3)
δ 7.32–7.27 (m, 4H), 7.03–7.00 (m, 2H); 13C NMR (75
MHz, CDCl3) δ 132.1, 127.6, 127.1, 122.9, 86.2; HRMS
m/z (ESI) calcd for C10H7S2: 190.9984, found: 190.9987
[M+H]+.
1,4-Di(quinolin-6-yl)buta-1,3-diyne (4d). Yellow solid;
yield 52%, 79 mg; m.p. 270–272 °C; 1H NMR (300 MHz,
CDCl3) δ 8.95–8.93 (m, 2H), 8.16–8.07 (m, 6H), 7.82–
7.79 (m, 2H), 7.48–7.43 (m, 2H); 13C NMR (75 MHz,
CDCl3) δ 151.5, 148.0, 135.8, 132.8, 132.2, 129.9, 127.9,
122.0, 119.9, 81.7, 75.0; IR (KBr) ν: 765, 793, 834, 897,
1115, 1316, 1349, 1400, 1490, 1631, 3430 cm-1; HRMS
m/z (ESI) calcd for C22H13N2: 305.1073, found: 305.1074
[M+H]+.
1,2-Bis(benzo[b]thiophen-5-yl)ethyne (3t).[32] Yellow
1
solid; yield 78%, 113 mg; m.p. 218–220 °C; H NMR
(300 MHz, CDCl3) δ 8.04 (s, 2H), 7.86 (d, J = 8.3 Hz, 2H),
7.53–7.48 (m, 4H), 7.34 (d, J = 5.4 Hz, 2H); 13C NMR (75
MHz, CDCl3) δ 139.6, 131.5, 127.33, 127.30, 126.9, 123.7,
122.5, 119.3, 89.2; HRMS m/z (ESI) calcd for C18H10S2:
290.0224, found: 290.0227 [M]+.
1,4-Di(isoquinolin-4-yl)buta-1,3-diyne (4e). Yellow solid;
yield 57%, 87 mg; m.p. 251–253 °C; 1H NMR (300 MHz,
CDCl3) δ 9.26 (s, 2H), 8.85 (s, 2H), 8.33 (d, J = 8.3 Hz,
2H), 8.04 (d, J = 8.2 Hz, 2H), 7.86 (t, J = 7.6 Hz, 2H),
7.71 (t, J = 7.7 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ
152.9, 148.2, 136.1, 131.6, 128.3, 128.2, 127.7, 125.0,
114.6, 80.6, 78.8; IR (KBr) ν: 749, 779, 796, 892, 1020,
1270, 1401, 1617, 1631, 2850, 2919, 3428 cm-1; HRMS
m/z (ESI) calcd for C22H13N2: 305.1073, found: 305.1065
[M+H]+.
1,2-Bis(2-thiazolyl)ethylene (3u).[19] Yellow solid; yield
69%, 66 mg; m.p. 143–144 °C; 1H NMR (300 MHz,
CDCl3) δ 7.94 (d, J = 3.3 Hz, 2H), 7.49 (d, J = 3.2 Hz,
2H); 13C NMR (75 MHz, CDCl3) δ 147.1, 144.2, 122.1,
86.0; HRMS m/z (ESI) calcd for C8H5N2S2: 192.9889,
found: 192.9890 [M+H]+.
1,2-Di(pyrimidin-2-yl)ethyne (3v). Yellow solid; yield
71%, 64 mg; m.p. 266–267 °C; 1H NMR (300 MHz,
CDCl3) δ 8.80 (d, J = 4.9 Hz, 4H), 7.33 (t, J = 4.9 Hz,
2H); 13C NMR (75 MHz, CDCl3) δ 157.3, 152.3, 120.6,
84.4; IR (KBr) ν: 793, 1351, 1400, 1631, 2852, 2923,
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701128
Advanced Synthesis & Catalysis
The competing coupling of aryl bromides with
trimethylsilylacetylene (Scheme 3)
mixture of ethyl acetate and petroleum ether (v:v, 1/6) as
the eluent to afford the pure product. The spectral data for
compounds 3ae and 3af are consistent with our published
paper.[17b]
The mixture of two aryl halides (1, 1.0 mmol) and
trimethylsilylethynylene (2a, 1.2 mmol), Pd(OAc)2 (4.6
mg, 0.02 mmol), Cu(Xantphos)I (15.4 mg, 0.02 mmol)
and Cs2CO3 (1.3 g, 4.0 mmol) in anhydrous DMF (3 mL)
2-(Phenylethynyl)pyrimidine (3av).[35] Yellow solid; yield
70%, 126 mg; m.p. 74–75 °C; 1H NMR (300 MHz,
CDCl3) δ 8.75 (d, J = 5.0 Hz, 2H), 7.82–7.66 (m, 2H),
7.42–7.36 (m, 3H), 7.24 (t, J =4.9 Hz, 1H); 13C NMR (75
MHz, CDCl3) δ 157.2, 153.2, 132.5, 129.6, 128.3, 121.2,
119.5, 87.8 (2C) ; HRMS m/z (ESI) calcd for C12H9N2:
181.0760, found: 181.0761 [M+H]+.
o
was heated at 60 C for 24 h under argon atmosphere.
After the reactions were completed, DMF was removed
under reduced pressure. The mixture was extracted with
ethyl acetate (3×15 mL) three times, and the combined
organic layers were dried over anhydrous Na2SO4 and
filtered. After removal of the solvent, the residue was
purified by flash column chromatography on silica gel
petroleum ether) as the eluent to afford the products. The
spectral data for compounds 3bc and 3ci are consistent
with our published paper.[17b]
(E)-1-methoxy-4-(4-phenylbut-3-en-1-yn-1-yl)benzene
(3cw).[36] Yellow solid; yield 58%, 136 mg; m.p. 49–
1
50 °C; H NMR (300 MHz, CDCl3) δ 7.41 (d, J = 8.7 Hz,
4H), 7.36–7.27 (m, 3H), 7.00 (d, J = 16.2 Hz, 1H), 6.87–
6.84 (m, 2H), 6.38 (d, J = 16.2 Hz, 1H), 3.82 (s, 3H); 13C
NMR (75 MHz, CDCl3) δ 159.6, 140.4, 136.5, 133.0,
128.7, 128.4, 126.2, 115.5, 114.0, 108.4, 91.8, 87.6, 55.3;
HRMS m/z (ESI) calcd for C17H15O: 235.1117, found:
235.1109 [M+H]+.
General procedure for one-pot synthesis of
unsymmetrical diarylalkynes 3ae, 3af, 3av and 3cw
(Scheme 4)
The mixture of aryl halides (1, 1.0 mmol) and
trimethylsilylacetylene (2a, 1.2 mmol), Pd(OAc)2 (4.6 mg,
0.02 mmol), Cu(Xantphos)I (15.4 mg, 0.02 mmol) and
Cs2CO3 (1.3 g, 4.0 mmol) in anhydrous toluene (2 mL)
was heated at 60 oC (for X = Br, 16 h) or room
temperature (for X = I, 12 h) under argon atmosphere,
then the solution of another aryl bromides in DMF (1 mL)
Acknowledgements
We gratefully acknowledge support from the National Natural
Science Foundation of China (21542009).
o
was added to the mixture at 60 C for 16 h. After the
reactions were completed, DMF was removed under
reduced pressure. The mixture was extracted with ethyl
acetate (3×15 mL) three times, and the combined organic
layers were dried over anhydrous Na2SO4 and filtered.
After removal of the solvent, the residue was purified by
flash column chromatography on silica gel using the
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10.1002/adsc.201701128
Advanced Synthesis & Catalysis
FULL PAPER
One-pot Domino Synthesis of Diarylalkynes/1,4-
Diaryl-1,3-diynes
by
[9,9-Dimethyl-4,5-
bis(diphenylphosphino)xanthene]Copper(I) Iodine–
Palladium(II) Acetate Catalyzed Double
Sonogashira-type Reaction
Adv. Synth. Catal. Year, Volume, Page – Page
Shaozhong Qiu,a Caiyang Zhang,a Rui Qiu,a
Guodong Yina,*and Jinkun Huangb,*
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