Gram-Scale Preparation of Pd@PANI: A Practical Catalyst Reagent for Copper-Free and Ligand-Free Sonogashira Couplings

Article abstract of DOI:10.1021/acs.oprd.6b00322

Palladium nanoparticles on the polyaniline (Pd@PANI) catalyst are now easily prepared on a gram scale through the oxidative polymerization of aniline in the presence of PdCl₂ by using air as a clean oxidant. The material is found to be very stable and can be stored for more than one year without deactivation. Thus, it may become a commercial reagent in organic synthesis, depending on its application scopes. This article reported the first example of Pd@PANI-catalyzed Sonogashira couplings free of copper and ligands.

Full text of DOI:10.1021/acs.oprd.6b00322

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Communication
Gram-Scale Preparation of Pd@PANI: A Practical Catalyst
Reagent for Copper-Free and Ligand-Free Sonogashira Couplings
Lei Yu, Zhe Han, and Yuanhua Ding
Org. Process Res. Dev., Just Accepted Manuscript • DOI: 10.1021/acs.oprd.6b00322 • Publication Date (Web): 18 Nov 2016
Downloaded from http://pubs.acs.org on November 21, 2016
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Gram-Scale Preparation of Pd@PANI: A Practical
Catalyst Reagent for Copper-Free and Ligand-Free
Sonogashira Couplings
Lei Yu,* Zhe Han and Yuanhua Ding
Jiangsu Co-innovation Center for Prevention and Control of Important Animal Infectious
Diseases and Zoonoses, Jiangsu Key Laboratory of Zoonosis, School of Chemistry and Chemical
Engineering, Yangzhou University, Yangzhou, 225002, People’s Republic of China.
KEYWORDS. Palladium, polyaniline, nanoparticles, Sonogashira coupling, copper-free.
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ABSTRACT. Palladium nanoparticles on polyaniline (Pd@PANI) catalyst is now easily
prepared in gram-scale through the oxidative polymerization of aniline in the presence of PdCl2
by using air as clean oxidant. The material is found to be very stable and can be stored for more
than one year without deactivation. Thus, it may become a commercial reagent in organic
synthesis, depending on its application scopes. This article reported the first example of
Pd@PANI-catalyzed Sonogashira couplings free of copper and ligand.
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Keywords: Polyaniline, Sonogashira coupling, palladium nanoparticle, ethisterone, phosphorus-
free
INTRODUCTION
Polymer-supported catalysts are important materials for their great application potential in
industrial production.1-3 Different from inorganic supporters, polymers could be well modified
through the introduction of specialized functional groups into their monomers, which provided
sufficiently variable factors for catalyst activity tunings. Among reported works, polyaniline2c,3-4
(PANI) are promising supporters because of their low-toxicity5 and availability. PANI-supported
metal catalysts (M@PANIs)2c,3 are readily accessible through the oxidative polymerization of
anilines in the presence of metal chlorides, which, in comparison with organometallic complexes,
are extremely cheap and available. M@PANIs may serve as an important class of catalysts in not
far future. But the field belongs to materials chemistry and attracts less attention from organic
chemists. Investigations on M@PANI catalysts mainly focused on the design of new materials,
while the applications in organic reactions are just a method to test their catalytic activities by
using very simple reactions with narrow application scopes.3 Currently, M@PANI catalysts have
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been applied in Suzuki cross-couplings, Heck reactions, the hydroxylation of aryl halides and
some redox reactions and cyclo-additions.2c,3
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On the other hand, Sonogashira cross-coupling is able to form a C-C bond between the
terminal sp hybridized carbon from an alkyne with a sp2 carbon of an aryl or vinyl halide.6 It is
one of the most important reactions in organic synthesis to prepare aryl alkynes and conjugated
enynes, which are important intermediates for the synthesis of many natural products,
pharmaceuticals and organic functional materials.7 A typical Sonogashira cross-coupling
employs ligand and copper salt as co-catalyst, which introduces in reaction another
environmentally unfriendly and difficult to recover reagent and leads to homo-coupling product
of the terminal alkyne.8 In line with the calls for greater environmental protection, the copper-
free and ligand-free Sonogashira cross-couplings using simplified catalyst are the trend of
development in the field.9
Our group aims to develop green technologies with industrial potential.2,10 In 2015, we
developed a novel method to fabricate the ultrasmall and uniform Pd@PANI catalyst by using
air as oxidant instead of the conventionally employed chemical oxidant.2c The catalyst was then
successfully employed in Heck reactions. Recently, gram-scale preparations of Pd@PANI have
been achieved. The light-yellow powder was obtained in good yield (85%) and was found to be
very stable (Figure 1). IPC analysis indicated that the weight ratio of Pd in the material was
0.85%. It could be stored under normal conditions for more than one year without deactivation,
indicating great potential for reagent development. After a series of conditional optimizations,
the Pd@PANI catalyst was successfully applied in copper-free and ligand-free Sonogashira
couplings for the first time. Herein, we wish to report our findings.
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Figure 1. Preparation of Pd@PANI in gram-scale.
RESULTS AND DISCUSSION
The reaction of iodobenzene 1a with phenylacetylene 2a was chosen as the model reaction for
conditional optimizations. For each reaction performed in 1 mmol scale, 0.6 mg of the catalyst
was employed. The catalyst loading was 0.005 mol % on the basis of the substrates, as calculated
according to the IPC analysis result. The reaction was first performed in DMF with excess Et3N,
but gave the product 3a in low yield (42 %, Table 1, entry 1). Reactions in other polar solvents,
such as NMP, DMSO, EtOH, EtOAc and MeCN were also tested and MeCN was screened out to
be the best one among them, giving 3a in 72 % yield (Table 1, entries 6 vs 2-5). The
coordination ability of the solvent might benefit the reaction in MeCN. Low-polar solvent, such
as THF, c-C6H12 and toluene, led to very poor results (Table 1, entries 7-9). The product yield
was further elevated to 86 % with extended reaction time (Table 1, entry 10).
Table 1. Optimization of the reaction conditiona
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Entry
Solvent
t (h)
24
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24
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24
24
48
3a yield / %b
1
2
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DMF
NMP
42
23
62
45
9
DMSO
EtOH
EtOAc
MeCN
THF
72
29
<3
<3
86
c-C6H12
toluene
MeCN
10
a
b
1 mmol of 1a, 1mmol of 2a, 0.5 mL of Et3N and 1.5 mL of solvent were employed.
Isolated yields.
Application scope of the reaction was then investigated. Electron-enriched aryl iodides were
obviously unfavorable for the reaction, giving alkynes 3b-d in decreased yields (Table 2, entries
2-4 vs. 1). In contrast, reactions of electron-deficient aryl iodides with phenylacetylene 2a
afforded the corresponding products 3e-k in generally good yields (Table 2, entries 5-11). In
several examples, such as the reactions of 3-NO2C6H4I and 2-FC6H4I, the products 3e-f were
obtained in excellent yields (Table 2, entries 5-6). Bulky 1-C10H7I could also lead to product 3l
in 81% yield (Table 2, entry 12). Nitrogen groups on the support PANI might serve as ligands of
palladium and thus enhanced the catalyst tolerance to hetero-elements in substrates (Table 2,
entries 13-14). Even 2-iodothiophene could react with 2a to give the desired product 3n in 70%
yield (Table 2, entry 14). The catalyst activity was low for sp2-C-Br activation and the reaction
of bromobenzene with 2a led to the product 3a in only 5% yield, but the product yields increased
for the reactions of electron-deficient aryl bromides (Table 2, entries 15-16). PhCOCl as
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substrate led to the desired product 3p in moderate yield (Table 2, entry 17). The application
scopes of terminal alkynes were also examined. Electron-enriched alkyne led to higher product
yield than the electron-deficient one (Table 2, entries 18 vs. 19). The catalyst was also applicable
for the reaction of aliphatic alkyne (Table 2, entry 20). A contrasting reaction of 3-NO2C6H4I
with phenylacetylene 2a catalyzed by 0.005 mol % of Pd/C led to 3e in only 26% yield (vs 96%,
Table 2, entry 5), showing that the Pd@PANI catalyst was obviously more active than traditional
heterogeneous catalyst.
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Table 2. Expanding the application scope of the Pd@PANI catalyzed Sonogashira reactionsa
Pd@PANI (0.005 mol %)
R1X + R2
1
H
R1
R2
80 oC, 48 h, N2
2
3
25 v/v % Et3N, MeCN
Entry
R1X
R2
3: yield / %b
1
2
PhI
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
3a: 86
3b: 52
3c: 61
3d: 50
3e: 96
3f: 96
3g: 77
3h: 70
3i: 72
3j: 57
3k: 50
3l: 81
3m: 40
2-MeC6H4I
3-MeC6H4I
4-MeC6H4I
3-NO2C6H4I
2-FC6H4I
3-FC6H4I
4-FC6H4I
4-ClC6H4I
4-BrC6H4I
4-AcC6H4I
1-C10H7I
3
4
5
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7
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9
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Ph
3n: 70
15
16
17
18
3-NO2C6H4Br
3,5-(CF3)2C6H3Br
PhCOCl
Ph
Ph
Ph
3e: 50
3o: 64
3p: 53
3d: 68
PhI
4-MeC6H4
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PhI
PhI
4-ClC6H4
3i: 10
c-C3H5
3q: 58
a
b
1 mmol of 1, 1mmol of 2, 0.5 mL of Et3N and 1.5 mL of MeCN were employed. Isolated
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yields.
Thus, as shown above, the Pd@PANI-catalyzed Sonogashira coupling has very wide substrate
scope. The material has already been employed as a mature catalyst reagent in our group during
some medicine development projects. For example, catalyzed by Pd@PANI and performed
under the optimized reaction conditions of Table 1, entry 10, the modification of ethisterone with
1.5 equivalent of PhI smoothly led to the desired product 3r in 52% yield (Scheme 1).
Ph
HO
HO
H
H
Pd@PANI
O
+ PhI
H
H
H
H
O
ethisterone
3r, 52%
Scheme 1. Pd@PANI-catalyzed modification of ethisterone.
As a heterogeneous catalyst, Pd@PANI could be recycled by centrifugalization and reused in
next turn of reaction. A 10 mmol scale reaction of 3-NO2C6H4I with 2a was tested. Because of
the reduction of Pd (II) to Pd (0),2c the color of the catalyst turned black after use. FTIR spectrum
of Pd@PANI also changed after use, but the catalysts used for multiple times possessed same
FTIR spectra (For details, please see S. I.). Results in Figure 2 clearly showed that the catalyst
could be recycled and reused for at least six times and the yield of product 3e was kept above
80%. Decrease of the product yield was probably due to the loss of ca. 2.4% of Pd loading of the
catalyst after using, as detected by ICP analysis. In addition, accumulate loss of Pd@PANI
during separation processes after each turn of reaction was also a probable reason, but in large-
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scale preparation, this issue could be resolved by a supplement of the lost catalyst.11 Moreover,
in the magnified experiment of the coupling of 3-NO2C6H4I with 2a at 124 mmol scale, the
product 3e was obtained in 84% yield (23.2 g) by recrystallization with EtOH, further confirming
the practicability of the method. ICP analysis indicated that the palladium residue in the product
was only 0.04 ppm.
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Figure 2. Recycle & reuse of the catalyst.
CONCLUSIONS
In conclusion, the first application of Pd@PANI in Sonogashira coupling was reported in this
paper, largely expanding the scope of this practical catalyst, which could be easiy prepared
through oxidative polymerization of aniline in the presence of PdCl2 by using air as clean
oxidant. The catalyst was very stable and could be stored under normal conditions for more than
one year without deactivation. Thus, it might serve as a mature catalyst reagent in future. More
investigations on challenging applications of this catalyst in organic synhteis are on the way in
our laboratory.
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EXPERIMENTAL SECTION
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General Methods. Reagents were purchased from reagent merchant with their purities more
than 98% and were directly used as received. Solvents were analytical pure (AR) and directly
used without any special treatment. Pd@PANI was prepared through oxidative polymerization of
aniline in the presence of PdCl2 by using air as clean oxidant and the detailed procedures were
given in our previous work.[6b] Melting points were measured by WRS-2A digital instrument. IR
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1
spectra were measured on Bruker Tensor 27 Infrared spectrometer. H and 13C NMR spectra
were recorded on a Bruker Avance 600/400 instrument (600 or 400 MHz for 1H and 150 or 100
MHz for 13C NMR spectroscopy) using CDCl3 as the solvent and Me4Si as the internal standard.
Chemical shifts for 1H and 13C NMR were referred to internal Me4Si (0 ppm) and J-values were
shown in Hz. Mass spectra were measured on a Shimadzu GCMS-QP2010 Ultra spectrometer
(EI). HRMS analysis was measured on a Waters GCT Premier instrument (EI-TOF) at Zhejiang
University.
Gram-scale preparation of Pd@PANI. 1.86 g PhNH2 (20 mmol) was dissolved in 200 mL of
aqueous HCl (1 M); 88.7 mg of PdCl2 (0.5 mmol) was dissolved in 200 mL of aqueous HCl (1
M); The above solutions were mixed and stirred at room temperature for 2 min and then stand for
24 h. The solution was neutralized to pH = 7 with aqueous NaOH (1 M) and the Pd@PANI
precipitated. The mixture was separated by filtration and the product was washed by deionized
water and baked at 100-110 oC for 1 h to afforded 1.66 g of Pd@PANI (85% yield).
General procedure for the Sonogashira reaction. To a reaction tube, 0.6 mg of Pd@PANI
catalyst was added. A solution of 1 mmol of ArX 1 and 1 mmol of alkyne 2 in 2 mL of
o
Et3N/MeCN (1:4) was then injected. The mixture was heated in N2 at 80 C for 48 h and then
cooled to room temperature. After evaporation of solvent, the residue was isolated by flash
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column chromatography on silica gel using petroleum ether as the eluent to give the products 3.
In the 10 mmol scale reaction of 3-NO2C6H4I with 2a, Pd@PANI was isolated by
centrifugalization and the supernatant liquid was subjected to flash column chromatography to
produce the pure product 3e.
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Procedure for the large-scale preparation of 3e. To a 500 mL three-necked flask, a magnetic
bar, 30.9 g of 3-NO2C6H4I (124 mmol), 6.64 g of phenylacetylene 2a (65 mmol, half portion), 80
mg of Pd@PANI, 70 mL of Et3N and 210 mL of MeCN were added. The flask was then charged
with N2 and stirred at 80 oC. After 24 h, another portion of phenylacetylene 2a (6.64g, 65 mmol)
was added and heated for another 24 h. The reaction mixture was cooled to room temperature
and filtrated by sand core funnel to recycle the catalyst. The filtrate was concentrated to
precipitate the product and recrystallization with EtOH led to product 3e in 84% yield (23.2 g).
Characterization data of the products
o
o
1,2-Diphenylethyne 3a. 153.1 mg, 86%; White soild, m.p. 62.5-63.2 C (lit. 63-64 C); IR
(KBr): 2979, 2869, 1951, 1599, 1494, 1442, 1141, 1069, 916, 755, 689 cm-1; 1H NMR (600 MHz,
CDCl3, TMS, ppm): δ 7.52-7.54 (m, 4H), δ 7.33-7.36 (m, 6H); 13C NMR (150 MHz, CDCl3,
ppm): δ 131.6, 128.3, 128.2, 123.3, 89.3; MS (EI, 70 eV): m/z (%) 179(27) [M++1], 178 (100)
[M+], 176 (36), 151 (20); Known compound (501-65-5).12a
o-Methylphenylphenylacetylene 3b. 100.0 mg, 52%; Oil; IR (film): 2360, 2335, 1599, 1571,
1
1493, 1455, 1379, 1157, 1103, 1069, 912, 754, 714, 689, 554, 521, 449 cm-1; H NMR (400
MHz, CDCl3, TMS, ppm): δ 7.45(s, 2H), 7.41(s, 1H), 7.25(s, 3H), 7.14(s, 2H), 7.07(s, 1H),
2.431(s, 3H); 13C NMR (100 MHz, CDCl3, ppm): δ 140.2, 131.9, 131.6, 129.5, 128.4 (d), 128.2,
125.6, 123.6, 123.1, 93.4, 88.4, 20.8; MS (EI, 70 eV): m/z (%) 192(97) [M+], 191 (100) [M+-1] ,
189 (36), 65 (26); Known compound (14309-60-5).12a
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m-Methylphenylphenylacetylene 3c. 117.3 mg, 61%; Oil; IR (film): 3033, 2920, 2858, 2360,
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2336, 2206, 1601, 1493, 1442, 1091, 1069, 1026, 913, 783, 754, 689, 544, 579, 440 cm-1; H
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NMR (600 MHz, CDCl3, TMS, ppm): δ 7.51 (d, J = 6.0 Hz, 2H), 7.36 - 7.31 (m, 5H), 7.22 (t, J =
7.2 Hz, 1H), 7.13 (d, J = 7.2 Hz, 1H), 2.34 (s, 3H); 13C NMR (150 MHz, CDCl3, ppm): δ 138.0,
132.1, 131.6, 129.2, 128.7, 128.3 (d), 128.2, 123.4, 123.1, 89.6, 89.1, 21.3; MS (EI, 70 eV): m/z
(%)193 (18) [M++1], 192 (100) [M+], 191 (41), 189 (29); Known compound (14635-91-7).12b
o
p-Methylphenylphenylacetylene 3d. 96.2 mg, 50%; White solid, m.p. 72.3-73.2 C (lit. 72-73
oC); IR (film): 2965, 2359, 1653, 1509, 1440, 1260, 1106, 1069, 915, 817, 755, 690, 515 cm-1;
1H NMR (600 MHz, CDCl3, TMS, ppm): δ 7.43 (s, 2H), 7.34(d, J = 6.0 Hz, 2H), 7.23 (s, 3H),
7.07 (s, 2H), 2.28 (s, 3H); 13C NMR (150 MHz, CDCl3, ppm): δ 137.3, 130.5, 130.4, 128.0,
127.2, 127.0, 122.4, 119.2, 88.5, 87.7, 20.4; MS (EI, 70 eV): m/z (%) 193 (15) [M++1], 192 (100)
[M+], 191 (49), 189 (23) ; Known compound (3287-02-3).12a
m-Nitrophenylphenylacetylene 3e. 214mg, 96%; Yellow soild, m.p. 68.5−70.1 °C (lit. 69-70
oC); IR (KBr): 3081, 2863, 2210, 1736, 1597, 1568, 1518, 1442, 1348, 1307, 919, 901, 812, 758,
736, 692, 673, 524, 460 cm-1; 1H NMR (600 MHz, CDCl3, TMS, ppm): δ 8.28 (s, 1H), 8.08 (d, J
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= 6.0 Hz, 1H), 7.73 (d, J = 4.2 Hz, 1H), 7.44 (t, J = 10.2 Hz, 3H), 7.30 (s, 3H); C NMR (150
MHz, CDCl3, ppm): δ 147.1, 136.2, 130.8, 128.3, 128.0, 127.5, 125.4, 124.2, 121.9, 121.2, 90.9,
85.9; MS (EI, 70 eV): m/z (%) 223 (69) [M+], 176 (100), 177 (48), 151 (34); Known compound
(29338-47-4).12a
o
o-Florophenylphenylacetylene 3f. 188.4mg, 96%; White soild, m.p. 45.8–47.0 C (lit. 45-47
oC); IR (KBr): 3060, 2214, 1938, 1794, 1596, 1571, 1498, 1451, 1262, 1220, 1158, 1097, 1031,
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939, 908, 856, 794, 749, 685, 521, 478 cm-1; H NMR (600 MHz, CDCl3, TMS, ppm): δ 7.56-
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7.50(m, 3H）, 7.36-7.29(m, 4H), 7.13-7.08(m, 2H); 13C NMR (150 MHz, CDCl3, ppm): 162.7 (d,
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JC-F = 250.1 Hz), 133.5, 131.7, 130.0 (d, JC-F = 8.0 Hz), 128.6, 128.4, 124.0 (d, JC-F = 3.6 Hz),
123.0, 115.6, 112.0 (d, JC-F = 15.6 Hz), 94.5, 82.7; MS (EI, 70 eV): m/z (%) 197 (50) [M++1],
196 (33) [M+], 195 (100), 193 (50); Known compound (29778-27-6).12c
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m-Florophenylphenylacetylene 3g. 151.1 mg, 77%. White soild, m.p. 35.2–37.0 oC (lit. 36 oC);
IR (film): 3065, 2212, 1607, 1579, 1494, 1432, 1316, 1262, 1206, 1118, 1071, 942, 870, 783,
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754, 688, 539, 517, 456 cm-1; H NMR (600 MHz, CDCl3, TMS, ppm): δ 7.52 (d, J = 4.8 Hz,
2H), 7.34-7.27 (m, 5H), 7.23-7.21 (m, 1H), 7.04-7.01 (m, 1H); 13C NMR (150 MHz, CDCl3,
ppm): 162.4 (d, JC-F = 245.0 Hz), 131.7, 129.9 (d, JC-F = 8.7 Hz), 128.6, 128.4, 127.5 (d, JC-F
=
3.2 Hz), 125.2 (d, JC-F = 9.5 Hz), 122.8, 118.4 (d, JC-F = 22.7 Hz), 115.5 (d, JC-F = 21.2 Hz), 90.3,
88.2; MS (EI, 70 eV): m/z (%) 197 (37) [M++1], 196 (100) [M+], 194 (35), 98 (25); Known
compound (29778-28-7).12c
o
p-Fluorophenylphenylacetylene 3h. 137.4 mg, 70%; White soild, m.p. 108.9–111.0 C (lit.
o
108-111 C); IR (KBr): 2930, 2854, 1579, 1477, 1450, 1355, 1087, 1023, 887, 763, 735, 701,
604, 464 cm-1; 1H NMR (600 MHz, CDCl3, TMS, ppm): δ 7.52-7.49 (m, 4H), 7.34-7.33(m, 3H),
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7.05-7.02 (m, 2H); C NMR (150 MHz, CDCl3, ppm): 162.5 (d, J = 247 Hz), 133.5 (d, J = 8.4
Hz), 131.6, 128.4 (d, J = 6.3Hz), 123.1, 119.4 (d, J = 3.6 Hz), 115.6(d, J = 21.9 Hz), 89.1, 88.2;
MS (EI, 70 eV): m/z (%) 197(16) [M++1], 196 (100) [M+], 194 (11), 98 (11); Known compound
(405-29-8).12a
p-Chlorophenylphenylacetylene 3i. 153.1mg, 72%; White soild. m.p. 82.6-83.5 oC (lit. 82-83
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oC); IR (KBr): 2854, 1683, 1493, 1440, 1398, 1089, 1013, 831, 756, 690, 514 cm-1; H NMR
(600 MHz, CDCl3, TMS, ppm): δ 7.45-7.44 (m, 2H), 7.38 (d, J = 8.4, 2H), 7.28-7.24 (m, 5H);
13C NMR (150 MHz, CDCl3, ppm): δ 134.2, 132.8, 131.6, 128.7, 128.40, 122.9, 121.8, 90.3,
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88.2; MS (EI, 70 eV): m/z (%) 213 (12) [M++1], 212 (100) [M+], 214 (32), 176 (31); Known
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compound (5172-02-1).12d
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p-Bromophenylphenylacetylene 3j. 146.5 mg, 57%; Yellow solid, m.p. 82.1-83.4 oC (lit. 82-83
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oC); IR (KBr): 2360, 2340, 1393, 1069, 827, 754 691, 512 cm-1; H NMR (600 MHz, CDCl3,
TMS, ppm): δ 7.52-7.51 (m, 2H), 7.48 (d, J = 9.2 Hz, 2H), 7.39 (d, J = 8.4 Hz, 2H), 7.35-7.34 (m,
3H); 13C NMR (150 MHz, CDCl3, ppm): δ 133.0, 131.6, 131.6, 128.5, 128.4, 122.9, 122.4, 122.3,
90.5, 88.3; MS (EI, 70 eV): m/z (%)257 (74) [M++1], 255 (74) [M+-1], 176 (100); Known
compound (13667-12-4).12e
p-Acetylphenylphenylacetylene 3k. 110.1 mg, 50%; Yellow soild, m.p. 100.1-101.2 °C (lit.
o
100-101 C); IR (KBr): 2922, 1679, 1600, 1441, 1402, 1359, 1264, 1108, 1070, 832, 761, 693,
591, 506, 449 cm-1; 1H NMR (400 MHz, CDCl3, TMS, ppm): δ 7.94(d, J = 8.4 Hz, 2H), 7.61(d, J
= 8.4 Hz, 2H), 7.54-7.56 (m, 2H), 7.36-7.37(m, 3H), 2.61(s, 3H); 13C NMR (100 MHz, CDCl3,
ppm): δ 197.4, 136.1, 131.7, 131.7, 128.8, 128.4, 128.3, 128.2, 122.6, 92.7, 88.6, 26.7; MS (EI,
70 eV): m/z (%) 220 (67) [M+], 205 (100), 206 (16), 176 (54); Known compound (1942-31-0).12a
1-(1-Naphthyl)-2-phenylacetylene 3l. 184.7mg, 81%; Yellow soild. m.p. 47-51°C; IR (film):
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3056, 1597, 1489, 1441, 1396, 798, 754, 688 cm-1; H NMR (600 MHz, CDCl3, TMS, ppm): δ
8.44(d, J = 8.4Hz, 1H), 7.84-7.80 (m, 2H), 7.74 (d, J=7.2 Hz, 1H), 7.64(d, J=7.2 Hz, 2H), 7.57 (t,
J = 7.5 Hz, 1H), 7.50(t, J = 7.5 Hz, 1H), 7.42 (t, J = 7.8Hz, 1H), 7.38-7.33 (m, 3H); 13C NMR
(150 MHz, CDCl3, ppm): δ 133.4, 133.3, 131.7, 130.4, 128.8, 128.5, 128.5, 128.4, 126.8, 126.5,
126.3, 125.3, 123.5, 121.0, 94.4, 87.6; MS (EI, 70 eV): m/z (%) 229 (20) [M++1], 228 (100) [M+],
112 (42), 226 (41) ; Known compound (4044-57-9).12b
2-(2-Phenylethynyl)pyridine 3m. 71.7 mg, 40%; Oil; IR (film): 2925, 2852, 1579, 1489, 1460,
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1425, 1384, 1150, 1025, 987, 914 cm-1; H NMR (600 MHz, CDCl3, TMS, ppm): δ 8.61(d, J =
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4.8Hz, 1H), 7.67 (t, J= 7.8 Hz, 1H), 7.61-7.59 (m, 2H), 7.52 (d, J = 7.8 Hz, 1H), 7.36-7.34(m,
3H), 7.24-7.22(m, 1H); 13C NMR (150 MHz, CDCl3, ppm): δ 150.0, 143.4, 136.2, 132.0, 129.0,
128.4, 127.1, 122.7, 122.2, 89.35, 88.5; MS (EI, 70 eV): m/z (%) 180 (15) [M++1], 179 (100)
[M+], 178 (43), 151 (16); Known compound (13141-42-9).12e
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2-(Phenylethynyl)thiophene 3n. 129.0 mg, 70%; Yellow solid, m.p. 50.4-51.2 °C (lit. 50-52 oC);
IR (KBr): 1596, 1486, 1441, 1213, 1110, 851, 831, 754 cm-1; 1H NMR (600 MHz, CDCl3, TMS,
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ppm): δ 7.52-7.50 (m, 2H), 7.35-7.32 (m, 3H), 7.29-7.25 (m, 2H), 7.00 (t, J = 9.0 Hz, 1H); C
NMR (150 MHz, CDCl3, ppm): δ 131.9, 131.4, 128.4, 128.3, 127.2, 127.1, 123.3, 122.9, 93.0,
82.6; MS (EI, 70 eV): m/z (%) 185 (14) [M++1], 184 (100) [M+], 139 (19), 152 (16); Known
compound (4805-17-8).12f
1-(Phenylethynyl)-3,5-bis(trifluoromethyl)benzene 3o. 201.1 mg, 64%; White solid, m.p.
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92 °C; IR (KBr): 1614, 1386, 1277, 1183, 1121, 916, 891, 844, 759, 692 cm-1; H NMR (600
MHz, CDCl3, TMS, ppm): δ 7.95 (s, 2H), 7.81 (s, 1H), 7.56-7.54 (m, 2H), 7.39 (d, J=7.2, 3H);
13C NMR (150 MHz, CDCl3, ppm): δ 132.1, 131.8, 131.4, 129.2, 128.5, 125.7, 123.8, 121.9,
121.5 (q, JC-F = 7.7 Hz), 92.8, 86.3; MS (EI, 70 eV): m/z (%) 315 (18) [M++1], 314 (100) [M+],
156 (17), 122 (14); Known compound (645411-85-4).12g
o
1,3-Diphenylprop-2-yn-1-one 3p. 109.2 mg, 53%; White solid, m.p. 49.1-50.3 C (lit. 49-50
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oC); IR (film): 3061, 1638, 1597, 1489, 1448, 1314, 1285, 1208, 1171, 1011, 920, 794 cm-1; H
NMR (600 MHz, CDCl3, TMS, ppm): δ 8.23 (d, J = 7.8 Hz, 2H), 7.68 (d, J = 7.2 Hz, 2H), 7.62 (t,
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J = 7.2 Hz, 1H), 7.53-7.40 (m, 5H); C NMR (150 MHz, CDCl3, ppm): δ 178.0, 136.9, 134.1,
133.0, 130.8, 129.5, 128.7, 128.6, 120.1, 93.1, 86.9; MS (EI, 70 eV): m/z (%) 206 (49) [M+], 128
(100) 129 (9); Known compound (7338-94-5).12h
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(Cyclopropylethynyl)benzene 3q. 82.4 mg, 58%; Oil; IR (film): 2924, 2853, 1733, 1699, 1652,
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1506, 1456, 1260, 1027, 954, 807 cm-1; H NMR (600 MHz, CDCl3, TMS, ppm): δ 7.29 (t, J =
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7.8Hz, 2H), 7.17 (d, J = 6.0 Hz, 3H), 1.38-1.34 (m, 1H), 0.80-0.71 (m, 4H); 13C NMR (150 MHz,
CDCl3, ppm): δ 131.5, 128.0, 127.3, 123.8, 93.3, 75.6, 29.6, 8.4; MS (EI, 70 eV): m/z (%) 142
(80) [M+], 141 (100), 115 (73), 114 (14); Known compound (21777-85-5).12i
(8R,9S,10R,13S,14S,17S)-17-hydroxy-10,13-dimethyl-17-(phenylethynyl)-
1,2,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-3H-cyclopenta[a]phenanthren-3-one 3t.
202.0 mg, 52%; White solid, m.p. 262.1-263.8 °C; IR (film): 3395, 2938, 1659, 1614, 1489,
1
1440, 1274, 1231, 1124, 1055, 757, 730, 692 cm-1; H NMR (400 MHz, CDCl3, TMS, ppm): δ
7.34 (d, J = 3.2 Hz, 2H), 7.23 (d, J = 2.4 Hz, 3H), 5.66 (s, 1H), 5.22 (s, 1H, OH) , 2.36-2.23 (m,
5H) , 2.01-1.96 (m, 3H) , 1.81-1.78 (m, 1H) , 1.71-1.58 (m, 5H), 1.52-1.47 (m, 2H), 1.37-1.29 (m,
2H), 1.14 (s, 3H), 0.88 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm): δ 199.7, 171.4, 131.6, 128.3,
123.9, 122.9, 92.6, 86.0, 80.1, 53.5, 50.2, 47.2, 39.0, 38.7, 36.3, 35.7, 34.0, 32.8 31.5, 29.7, 23.2,
20.8, 17.5, 13.0; LCMS (EI, 70 eV): 389.15 [M+H+]; HRMS for C27H32O2 calcd. 388.2402,
found 388.2406.
ASSOCIATED CONTENT
Supporting Information. Detailed experimental procedures and compound characterization
data and spectra. This material is available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: yulei@yzu.edu.cn
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ACKNOWLEDGMENT
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This work was supported by NNSFC (21202141, 21173182), Priority Academic Program
Development (PAPD) of Jiangsu Higher Education Institutions, Yangzhou Nature Science
Foundation (YZ2014040), the Open Project Program of Jiangsu Key Laboratory of Zoonosis
(R1509), the Innovation Foundation of Yangzhou University (2015CXJ009) and the High Level
Talent Support Project of Yangzhou University. We thank the analysis centre of Yangzhou
University for assistances.
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(10) For selected articles, please see: (a) Deng, S.-C.; Meng, T.-T.; Xu, B.-L.; Gao, F.; Ding, Y.-
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(11) The catalyst loadings are too low. Only 6 mg of Pd@PANI catalyst was employed even in
the magnified 10 mol scale reaction. Therefore, it is impossible to accurately measure the
lost catalyst weight after reaction. But in further large-scale reactions in future, the issue
could be resolved, like our previous works described in ref. 2b and 2d.
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