Stereoselective synthesis of functionalized (1E,5E)-1,5-dien-3-ynes containing ester or sulfonyl groups by palladium-catalyzed addition and cross-coupling reactions

Article abstract of DOI:10.1039/c4nj00087k

Trimethylsilylacetylene undergoes clean cis-addition to alkynyl sulfones or esters 1 in the presence of catalytic palladium acetate and tri(2,6-dimethoxyphenyl)phosphine to give (E)-1-sulfonyl (or ethoxycarbonyl)-4-trimethylsilyl-substituted 1,3-enyne 2 i

Full text of DOI:10.1039/c4nj00087k

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Stereoselective synthesis of functionalized (1E,5E)-
1,5-dien-3-ynes containing ester or sulfonyl
groups by palladium-catalyzed addition and
cross-coupling reactions
Cite this: New J. Chem., 2014,
38, 2686
Wenyan Hao, Shiyun Xie, Yichao Wu and Mingzhong Cai*
Trimethylsilylacetylene undergoes clean cis-addition to alkynyl sulfones or esters 1 in the presence of
catalytic palladium acetate and tri(2,6-dimethoxyphenyl)phosphine to give (E)-1-sulfonyl (or ethoxycarbonyl)-
4-trimethylsilyl-substituted 1,3-enyne 2 in excellent yields. The cross-coupling reaction of (E)-1-sulfonyl (or
ethoxycarbonyl)-4-trimethylsilyl-substituted 1,3-enyne 2 with (E)-alkenyl iodides 3 in the presence of
Pd(PPh3)4 and tris(diethylamino)sulfonium trimethyldifluorosilicate (TASF) affords stereoselectively (1E,5E)-
1-sulfonyl (or ethoxycarbonyl)-substituted 1,5-dien-3-ynes 4 in good yields.
Received (in Montpellier, France)
20th January 2014,
Accepted 23rd March 2014
DOI: 10.1039/c4nj00087k
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alkenyl iodides to give terminal 1,5-dien-3-ynes.11b Hoshi and
co-workers reported that alka-1,5-dien-3-ynes could be synthesized
Introduction
Construction of conjugated compounds, such as enynes, stereoselectively via a sequential Suzuki-type and Sonogashira
enediynes, and dienynes, is of great significance since they reaction of alkenyldisiamylborane with trimethylsilylethynyl bro-
are found in diverse fields ranging from natural products1 and mide and alkenyl iodides in a one-pot manner.11d
pharmaceuticals2 to functional materials.3 Furthermore, con-
The synthesis of dienynes containing metal or heteroatom
jugated molecules are versatile building blocks for many natu- functional groups has also attracted considerable interest in
rally occurring biologically active compounds and p-conjugated organic synthesis because many useful functional group trans-
polymers.4 In particular, the high p-electron delocalization formations can be achieved by introduction and removal of
behavior in these p-conjugated molecules enables their wide metal or heteroatom functions. Alami et al. reported the regio-
application in advanced organic materials, such as molecular selective synthesis of stannylated dienynes by the palladium-
wires, nonlinear optics, organic conductors, electrolumines- catalyzed hydrostannylation of enediynes.12 Liu and coworkers
cence, etc.4g,5 For the formation of sp–sp2 carbon–carbon reported that 2,5-di(trimethylsilyl)-substituted (1E,5E)-1,5-dien-
bonds, the transition metal-catalyzed cross-coupling reaction 3-ynes could be obtained with high stereoselectivity via the
is the key step.6 Suzuki reaction,7 Sonogashira reaction,8 Stille Brønsted acid catalyzed dehydration of cumulenols.13 Function-
reaction9 and Negishi reaction10 are used complementarily in alized 1,5-dien-3-ynes could also be prepared by transition metal-
such construction. A number of stereoselective methods for catalyzed bond reorganization of 1,3-diynes.14 Very recently,
obtaining conjugated dienynes have been described,11 gener- Jiang and co-workers reported the synthesis of various dihalo-,
ally, the key steps were two sequential palladium-catalyzed haloacyl-, and diacyl-substituted 1,5-dien-3-ynes by palladium-
cross-couplings between an acetylenic derivative and two alkenyl catalyzed bond reorganization of 1,3-diynes bearing propargylic
units. Hiyama and co-workers reported that trimethylsilyl(trimethyl- alcohol moieties.15 Despite the significant progress that has
stannyl)ethyne could couple sequentially with two different alkenyl been achieved in the synthesis of functionalized 1,5-dien-3-
iodides in the presence of the same palladium catalyst to afford ynes,12–15 further advances are still desirable, particularly with
stereo-defined 1,5-dien-3-ynes in one-pot.11a Rossi and co-workers regard to the controlled incorporation of different functional
converted trimethylsilylethynylzinc chloride into alka-1,5-dien-3-yne groups by a simple and convenient protocol. To the best of our
using the stepwise procedure, coupling with alkenyl halide, knowledge, no well-established method is used to prepare
desilylation, and coupling with another alkenyl halide.11c Tellier stereoselectively (1E,5E)-1-sulfonyl (or ethoxycarbonyl)-substituted
and co-workers reported that butenynylzinc bromides derived 1,5-dien-3-ynes. Herein, we wish to report that (1E,5E)-1-sulfonyl
from 1,1-difluoroethene underwent the Negishi coupling with (or ethoxycarbonyl)-substituted 1,5-dien-3-ynes could be conveni-
ently synthesized via the cis-addition of trimethylsilylacetylene to
alkynyl sulfones or esters in the presence of catalytic palladium
acetate and tri(2,6-dimethoxyphenyl)phosphine (2,6-TDMPP),
Department of Chemistry, Jiangxi Normal University, Nanchang 330022,
P. R. China. E-mail: mzcai@jxnu.edu.cn
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Scheme 1 Synthesis of functionalized 1,5-dien-3-ynes containing ester or sulfonyl groups.
followed by the cross-coupling reaction with (E)-alkenyl iodides 99%. One olefinic proton signal for compounds 2a–2g appears
in the presence of Pd(PPh3)4 and tris(diethylamino)sulfonium as a singlet at d = 5.87–6.71, which indicates that the addition
trimethyldifluorosilicate (TASF) (Scheme 1).
reaction of trimethylsilylacetylene to alkynyl sulfones or alkynyl
esters 1 had taken place with strong preference for the addition
of the hydrogen atom at the carbon adjacent to the phenyl-
sulfonyl or ester groups. The (1E)-configuration of the compound
2b was confirmed by the NOESY in the 1H NMR spectrum.
A correlation between the allylic protons (d = 2.49) and aromatic
protons was observed. There was no correlation between the
vinylic proton (d = 6.36) and the allylic protons (d = 2.49). The
NOE results indicate that compound 2b has the expected
E-configuration and that trimethylsilylacetylene undergoes clean
cis-1,2-addition to an internal alkynyl sulfone or alkynyl ester
in the presence of catalytic Pd(OAc)2 and 2,6-TDMPP in
1,2-dichloroethane.
The cross-coupling of organosilicon reagents with organic
halides has evolved to be comparable in scope to other
palladium-catalyzed coupling methods.18 Alkynylsilanes, which
are easily prepared by addition of alkynyllithium or alkynyl-
magnesium reagents to chlorosilanes, are competent reagents
for the palladium-catalyzed cross-coupling reaction.19 Hiyama
et al. reported that the palladium-catalyzed cross-coupling
reaction of alkynylsilanes with alkenyl halides could proceed
smoothly in the presence of tris(diethylamino)sulfonium tri-
methyldifluorosilicate (TASF) to afford the desired 1,3-enynes
in good yields.11a,19a To prepare highly stereoselectively (1E,5E)-
1-sulfonyl (or ethoxycarbonyl)-substituted 1,5-dien-3-ynes, we
investigated the palladium-catalyzed cross-coupling reaction of
(E)-1-sulfonyl (or ethoxycarbonyl)-4-trimethylsilyl-substituted
1,3-enynes 2 with (E)-alkenyl iodides 3 (Scheme 1). Our initial
efforts were devoted to the selection of an efficient catalyst and
a suitable solvent for the efficient cross-coupling reaction of
(E)-1-sulfonyl (or ethoxycarbonyl)-4-trimethylsilyl-substituted 1,3-
enynes 2 with (E)-alkenyl iodides 3. Thus, (E)-1-phenylsulfonyl-2-
butyl-4-trimethylsilyl-1-buten-3-yne 2a (1.2 mmol) and (E)-1-iodo-1-
hexene (1.0 mmol) were treated in different solvents (5 mL), at 50 1C,
with Pd(0) and Pd(II) catalysts in the presence of TASF
(1.5 mmol) (Table 2). As shown in Table 2, among the palla-
dium catalysts tested [PdCl2(MeCN)2, Pd(PPh3)4, PdCl2(PPh3)2,
and PdCl2(dppf)], Pd(PPh3)4 proved to be the most efficient. For
the solvents evaluated [DMF, THF, dioxane, and HMPA], THF
was the best choice. A lower yield was observed and a longer
reaction time was required when the amount of Pd(PPh3)4 was
decreased (entries 8 and 9). Taken together, good result was
Results and discussion
One general method for the synthesis of 1-sulfonyl-substituted
1,3-enynes involves the condensation of methyl phenyl sulfone
with a,b-acetylenic aldehydes or ketones in the presence of a base
and the subsequent dehydration of the condensation products
using methylsulfonyl chloride and triethylamine as dehydrating
agents, but low yields and poor stereoselectivity are usually
obtained.16 Trost et al. reported that terminal alkynes could
undergo clean cis-1,2-addition to alkynyl esters in the presence
of catalytic Pd(OAc)2 and tri(2,6-dimethoxyphenyl)phosphine to
produce 2-en-4-ynoates in excellent yields.17 We also found that
the cis-addition reaction of trimethylsilylacetylene to alkynyl
sulfones or esters 1 could proceed smoothly in the presence of
2 mol% of Pd(OAc)2 and 2 mol% of tri(2,6-dimethoxyphenyl)-
phosphine (2,6-TDMPP) in 1,2-dichloroethane at room tempera-
ture to afford highly regio- and stereoselectively (E)-1-sulfonyl
(or ethoxycarbonyl)-4-trimethylsilyl-substituted 1,3-enynes 2 in
excellent yields after 6 h (Scheme 1). The typical results are
summarized in Table 1. As shown in Table 1, a variety of alkynyl
sulfones and alkynyl esters could be used as the substrates and
the isolation of products only involved direct flash chromato-
graphy to give the desired (E)-1-sulfonyl (or ethoxycarbonyl)-4-
trimethylsilyl-substituted 1,3-enynes 2.
1
Investigations of the crude products 2 by H NMR spectro-
scopy (400 MHz) showed their isomeric purities of more than
Table 1 Synthesis of (E)-1-sulfonyl (or ethoxycarbonyl)-4-trimethylsilyl-
substituted 1,3-enynes 2a
Entry
EWG
R
Product
Yieldb (%)
1
2
3
4
5
6
7
SO2Ph
SO2Ph
SO2Ph
SO2Ph
CO2Et
CO2Et
CO2Et
n-C4H9
n-C6H13
Ph
CH3OCH2CH2
n-C4H9
Ph
2a
2b
2c
2d
2e
2f
89
90
91
86
90
91
88
Cyclopropyl
2g
a
Reaction conditions: trimethylsilylacetylene (1.1 mmol), alkynyl sul-
fone or ester (1 mmol), Pd(OAc)2 (0.02 mmol), 2,6-TDMPP (0.02 mmol),
b
1,2-dichloroethane (2 mL), room temperature, 6 h. Isolated yields.
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Table 2 Influences of the catalysts and solvents in the cross-coupling reactiona
Entry
Catalyst (mol%)
Solvent
Time (h)
Isolated yield 4a (%)
1
2
3
4
5
6
7
8
9
PdCl2(MeCN)2 (5)
Pd(PPh3)4 (5)
PdCl2(PPh3)2 (5)
PdCl2(dppf) (5)
Pd(PPh3)4 (5)
Pd(PPh3)4 (5)
Pd(PPh3)4 (5)
Pd(PPh3)4 (2.5)
Pd(PPh3)4 (1)
THF
THF
THF
THF
DMF
Dioxane
HMPA
THF
4
2
4
4
4
4
4
6
24
54
84
60
62
69
59
73
80
75
THF
a
Reaction was performed with 2a (1.2 mmol), (E)-1-iodo-1-hexene (1.0 mmol), TASF (1.5 mmol), solvent (5 mL) at 50 1C under Ar.
obtained when the cross-coupling reaction was carried out with 1,3-enynes 2 with (E)-alkenyl iodides 3 under the same reaction
5 mol% Pd(PPh3)4 in THF in the presence of TASF (1.5 equiv.) at conditions (Table 3, entries 8–14). In all cases, a single geometric
50 1C for 2 h under an Ar atmosphere (entry 2).
isomer was formed as shown in Scheme 1. The (5E)-configuration
To examine the scope of this cross-coupling reaction, the of the compounds 4a–4n has been proved by their 1H NMR
coupling reactions of a variety of (E)-1-sulfonyl (or ethoxy- spectra which showed a doublet at d = 5.46–6.32 with a coupling
carbonyl)-4-trimethylsilyl-substituted 1,3-enynes 2 with various constant of 16.0–16.4 Hz, and this is also the evidence of the
(E)-alkenyl iodides 3 were investigated under the optimum retention of the E-configuration of the starting compounds 3.
conditions and the experimental results are listed in Table 3.
We also attempted a one-pot bis-functionalization of trimethyl-
As shown in Table 3, the palladium-catalyzed cross-coupling silylacetylene. After the addition reaction of trimethylsilylacetylene
reactions of a variety of (E)-1-sulfonyl-4-trimethylsilyl-substituted (1.1 equiv.) with 1-phenylsulfonyl-1-hexyne using 2 mol% Pd(OAc)2
1,3-enynes 2 with (E)-alkenyl iodides 3 proceeded smoothly in and 2 mol% tri(2,6-dimethoxyphenyl)phosphine (2,6-TDMPP) in
the presence of 5 mol% Pd(PPh3)4 and TASF (1.5 equiv.) in THF 1,2-dichloroethane at room temperature for 6 h, (E)-1-iodo-1-
at 50 1C to afford highly stereoselectively the corresponding (1E,5E)- hexene (1.0 equiv.) and TASF (1.5 equiv.) were added and the
1-sulfonyl-substituted 1,5-dien-3-ynes 4a–g in good yields (Table 3, mixture was stirred at 80 1C for 24 h, unfortunately, the desired
entries 1–7). Similarly, stereo-defined (1E,5E)-1-ethoxycarbonyl- coupling product 4a was not obtained. Even if the reaction
substituted 1,5-dien-3-ynes 4h–n could also be conveniently temperature was reduced to 60 or 50 1C, no desired 4a was
obtained in good yields by the palladium-catalyzed cross-coupling observed. We then examined the effect of the solvents on the
reactions of (E)-1-ethoxycarbonyl-4-trimethylsilyl-substituted secondary transformation. It was found that, after the addition
Table 3 Synthesis of (1E,5E)-1-sulfonyl (or ethoxycarbonyl)-substituted 1,5-dien-3-ynes 4a
Entry
EWG
R
R1
Product
Yieldb (%)
1
2
3
4
5
6
7
8
SO2Ph
SO2Ph
SO2Ph
SO2Ph
SO2Ph
SO2Ph
SO2Ph
CO2Et
CO2Et
CO2Et
CO2Et
CO2Et
CO2Et
CO2Et
n-C4H9
n-C4H9
Ph
n-C6H13
n-C6H13
n-C6H13
Ph
n-C4H9
n-C4H9
Ph
n-C4H9
Ph
Ph
4a
4b
4c
4d
4e
4f
4g
4h
4i
4j
4k
4l
4m
4n
84
79
80
83
76
74
78
86
81
83
80
77
75
82
Ph
n-C4H9
CH3OCH2CH2
CH3OCH2CH2
Ph
n-C6H13
Ph
n-C6H13
Ph
n-C4H9
CH3OCH2CH2
9
10
11
12
13
14
Ph
Cyclopropyl
Cyclopropyl
n-C4H9
a
Reaction was performed with 2 (1.2 mmol), 3 (1 mmol), Pd(PPh3)4 (0.05 mmol), TASF (1.5 mmol), THF (5 mL) at 50 1C under Ar for 2 h.
Isolated yields.
b
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reaction of trimethylsilylacetylene (1.1 equiv.) with 1-phenyl- 1H NMR (400 MHz, CDCl3) d (ppm): 7.73 (d, J = 7.2 Hz, 2H), 7.45–
sulfonyl-1-hexyne using 2 mol% Pd(OAc)2 and 2 mol% tri(2,6- 7.35 (m, 3H), 6.36 (s, 1H), 2.49 (t, J = 7.2 Hz, 2H), 1.33–1.30
dimethoxyphenyl)phosphine (2,6-TDMPP) in 1,2-dichloroethane at (m, 2H), 1.19–1.13 (m, 2H), 0.72 (t, J = 7.2 Hz, 3H), 0.00 (s, 9H).
room temperature for 6 h, solvent removal under reduced pressure 13C NMR (100 MHz, CDCl3) d (ppm): 141.8, 140.4, 134.4, 133.3,
and stirring of the residue with THF, (E)-1-iodo-1-hexene 129.2, 127.4, 103.1, 102.9, 31.1, 30.2, 22.2, 13.7, À0.52. Anal.
(1.0 equiv.) and TASF (1.5 equiv.) at 50 1C for 24 h, only trace calcd for C17H24O2SiS: C, 63.72; H, 7.55. Found: C, 63.46; H, 7.31.
amounts of desired 4a was detected. The other solvents such as
dioxane, DMF, and HMPA were also found to be ineffective.
(E)-1-Phenylsulfonyl-2-hexyl-4-trimethylsilyl-1-buten-3-yne 2b
[Table 1, entry 2]. Oil. IR (neat): nmax/cmÀ1 2931, 2860, 2147,
1576, 1447, 1308, 1252, 1151, 1086, 845, 723, 605. 1H NMR
(400 MHz, CDCl3) d (ppm): 7.74–7.72 (m, 2H), 7.45–7.35
(m, 3H), 6.36 (s, 1H), 2.49 (t, J = 7.6 Hz, 2H), 1.35–1.30
(m, 2H), 1.18–1.04 (m, 6H), 0.70 (t, J = 7.2 Hz, 3H), 0.00
(s, 9H). 13C NMR (100 MHz, CDCl3) d (ppm): 142.2, 141.1,
134.8, 133.9, 129.7, 127.9, 103.4, 103.3, 32.0, 31.8, 29.2, 28.5,
22.9, 14.5, 0.0. Anal. calcd for C19H28O2SiS: C, 65.48; H, 8.10.
Found: C, 65.21; H, 7.82.
(E)-1-Phenylsulfonyl-2-phenyl-4-trimethylsilyl-1-buten-3-yne 2c
[Table 1, entry 3]. Oil. IR (neat): nmax/cmÀ1 3060, 2926, 2215, 1562,
1447, 1307, 1251, 1151, 1085, 843, 722. 1H NMR (400 MHz, CDCl3)
d (ppm): 7.45 (d, J = 7.6 Hz, 2H), 7.35 (t, J = 7.4 Hz, 1H), 7.23–7.12
(m, 7H), 6.71 (s, 1H), 0.00 (s, 9H). 13C NMR (100 MHz, CDCl3)
d (ppm): 141.3, 137.9, 136.7, 134.4, 133.8, 130.3, 129.6, 129.4,
128.4, 128.3, 104.6, 103.4, 0.0. Anal. calcd for C19H20O2SiS: C,
67.03; H, 5.92. Found: C, 66.77; H, 5.69.
Conclusion
In summary, we have developed a highly efficient approach for
the stereoselective synthesis of functionalized (1E,5E)-1,5-dien-
3-ynes containing ester and sulfonyl groups by the cis-addition
of trimethylsilylacetylene to alkynyl sulfones or esters in the
presence of catalytic palladium acetate and tri(2,6-dimethoxy-
phenyl)phosphine (2,6-TDMPP), followed by the palladium-
catalyzed cross-coupling reaction with (E)-alkenyl iodides in
the presence of TASF. The present method has some attractive
advantages of readily available starting materials, straight-
forward and simple procedures, mild reaction conditions, high
stereoselectivity and good yields.
(E)-1-Phenylsulfonyl-2-(2-methoxyethyl)-4-trimethylsilyl-1-buten-
3-yne 2d [Table 1, entry 4]. Oil. IR (neat): nmax/cmÀ1 2961, 2890,
2345, 1586, 1449, 1304, 1251, 1149, 1119, 1087, 849, 607. 1H NMR
(400 MHz, CDCl3) d (ppm): 7.76 (d, J = 7.2 Hz, 2H), 7.45–7.35
(m, 3H), 6.40 (s, 1H), 3.43 (t, J = 6.4 Hz, 2H), 3.15 (s, 3H), 2.84 (t, J =
6.4 Hz, 2H), 0.00 (s, 9H). 13C NMR (100 MHz, CDCl3) d (ppm):
141.2, 136.7, 136.0, 133.6, 129.3, 127.6, 103.6, 102.1, 70.1, 58.7,
31.3, À0.45. Anal. calcd for C16H22O3SiS: C, 59.61; H, 6.88.
Found: C, 59.38; H, 7.02.
(E)-1-(Ethoxycarbonyl)-2-butyl-4-trimethylsilyl-1-buten-3-yne
2e [Table 1, entry 5]. Oil. IR (neat): nmax/cmÀ1 2960, 2933, 2874,
2145, 1717, 1610, 1466, 1368, 1252, 1193, 1146, 1037, 844, 760.
1H NMR (400 MHz, CDCl3) d (ppm): 5.87 (s, 1H), 3.95 (q, J =
7.2 Hz, 2H), 2.52 (t, J = 7.6 Hz, 2H), 1.40–1.29 (m, 2H), 1.21–1.09
(m, 2H), 1.07 (t, J = 7.2 Hz, 3H), 0.72 (t, J = 7.4 Hz, 3H), 0.00
(s, 9H). 13C NMR (100 MHz, CDCl3) d (ppm): 165.8, 142.8, 124.7,
105.6, 99.9, 60.0, 31.7, 30.5, 22.3, 14.2, 13.9, À0.3. Anal. calcd
for C14H24O2Si: C, 66.64; H, 9.59. Found: C, 66.37; H, 9.33.
(E)-1-(Ethoxycarbonyl)-2-phenyl-4-trimethylsilyl-1-buten-3-yne
2f [Table 1, entry 6]. Oil. IR (neat): nmax/cmÀ1 2961, 2901, 2139,
1726, 1597, 1445, 1369, 1251, 1160, 1085, 1034, 845, 761.
Experimental
General comments
All chemicals were of reagent grade and used as purchased. All
solvents were dried and distilled before use. The products were
purified by flash chromatography on silica gel. A mixture of
light petroleum ether (30–60 1C) and diethyl ether was generally
used as the eluent. All products were characterized by compar-
ison of their spectra and physical data with authentic samples.
IR spectra were determined on a Perkin-Elmer 683 instrument.
1H NMR spectra were recorded on a Bruker Avance 400 (400 MHz)
spectrometer with TMS as an internal standard in CDCl3 as the
solvent. 13C NMR spectra were recorded on a Bruker Avance 400
(100 MHz) spectrometer in CDCl3 as the solvent. Mass spectra
were obtained on a Finnigan 8239 mass spectrometer. Micro-
analyses were done using a Yanaco MT-3 CHN microelemental
analyzer. Alkynyl sulfones20 and alkynyl esters21 were prepared
according to literature procedures.
General procedure for the palladium-catalyzed addition reaction
of trimethylsilylacetylene to alkynyl sulfones or esters
To a solution of alkynyl sulfone or alkynyl ester (1.0 mmol) and 1H NMR (400 MHz, CDCl3) d (ppm): 7.24–7.21 (m, 2H), 7.14–
trimethylsilylacetylene (1.1 mmol) in 1,2-dichloroethane (2.0 mL) 7.12 (m, 3H), 6.13 (s, 1H), 3.86 (q, J = 7.2 Hz, 2H), 0.92 (t, J =
Pd(OAc)2 (0.02 mmol) and 2,6-TDMPP (0.02 mmol) were added 7.2 Hz, 3H), 0.00 (s, 9H). 13C NMR (100 MHz, CDCl3) d (ppm):
at room temperature under an argon atmosphere. The reaction 165.3, 137.7, 136.2, 128.9, 128.6, 127.8, 125.6, 105.1, 101.0, 60.4,
mixture was stirred at room temperature for 6 h and concen- 13.9, À0.3. Anal. calcd for C16H20O2Si: C, 70.57; H, 7.40. Found:
trated under reduced pressure and the residue was purified by C, 70.71; H, 7.56.
column chromatography (light petroleum ether/diethyl ether,
3 : 1 or 10: 1) on silica gel.
(E)-1-(Ethoxycarbonyl)-2-cyclopropyl-4-trimethylsilyl-1-buten-
3-yne 2g [Table 1, entry 7]. Oil. IR (neat): nmax/cmÀ1 2961, 2902,
(E)-1-Phenylsulfonyl-2-butyl-4-trimethylsilyl-1-buten-3-yne 2a 2150, 1712, 1598, 1395, 1384, 1252, 1155, 1042, 920, 857, 734.
[Table 1, entry 1]. Oil. IR (neat): nmax/cmÀ1 3066, 2960, 2932, 1H NMR (400 MHz, CDCl3) d (ppm): 6.09 (s, 1H), 4.18 (q, J =
2873, 2145, 1576, 1447, 1307, 1251, 1150, 1085, 844, 724, 605. 7.2 Hz, 2H), 3.16–3.12 (m, 1H), 1.28 (t, J = 7.2 Hz, 3H), 0.93–0.86
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(m, 4H), 0.19 (s, 9H). 13C NMR (100 MHz, CDCl3) d (ppm): 166.4, (400 MHz, CDCl3) d (ppm): 7.93 (d, J = 7.6 Hz, 2H), 7.63–7.53
145.8, 123.2, 101.1, 99.8, 59.8, 14.2, 12.0, 8.4, À0.4. Anal. calcd (m, 3H), 7.40–7.33 (m, 5H), 7.01 (d, J = 16.0 Hz, 1H), 6.55 (s, 1H),
for C13H20O2Si: C, 66.08; H, 8.53. Found: C, 65.86; H, 8.72.
6.26 (d, J = 16.0 Hz, 1H), 2.72 (t, J = 7.6 Hz, 2H), 1.58–1.50
(m, 2H), 1.30–1.21 (m, 6H), 0.89 (t, J = 7.0 Hz, 3H). 13C NMR
(100 MHz, CDCl3) d (ppm): 144.2, 142.0, 141.1, 135.6, 133.4,
133.1, 129.4, 129.3, 128.9, 127.4, 126.6, 106.7, 96.2, 90.2, 31.6,
31.5, 28.9, 28.3, 22.5, 14.1. MS (EI, 70 eV): m/z (%) = 378 (26)
General procedure for palladium-catalyzed cross-coupling of
(E)-1-sulfonyl (or ethoxycarbonyl)-4-trimethylsilyl-substituted
1,3-enynes 2 with (E)-alkenyl iodides 3
A THF solution of TASF (1.0 M, 1.5 mL, 1.5 mmol) was added to [M]+, 308 (36), 247 (78), 165 (65), 77 (100), 57 (45). Anal. calcd for
(E)-1-sulfonyl (or ethoxycarbonyl)-4-trimethylsilyl-substituted C24H26O2S: C, 76.15; H, 6.92. Found: C, 75.87; H, 6.70.
1,3-enyne 2 (1.2 mmol) and Pd(PPh3)4 (0.05 mmol) dissolved
(1E,5E)-1-Phenylsulfonyl-2-hexyl-1,5-decadien-3-yne 4e [Table 3,
in THF (3.5 mL) at À78 1C under an argon atmosphere. (E)-Alkenyl entry 5]. Oil. IR (neat): nmax/cmÀ1 2959, 2929, 2188, 1574, 1447,
iodide 3 (1.0 mmol) was injected to the resulting solution, and the 1317, 1149, 1085, 958, 821, 753. 1H NMR (400 MHz, CDCl3) d
mixture was slowly warmed to ambient temperature, and allowed (ppm): 7.91 (d, J = 7.6 Hz, 2H), 7.64–7.52 (m, 3H), 6.48 (s, 1H), 6.25
to react for 2 h at 50 1C. After being cooled to room temperature, (dt, J = 16.0, 7.6 Hz, 1H), 5.59 (d, J = 16.0 Hz, 1H), 2.67 (t, J = 7.6 Hz,
the mixture was quenched with aq. sodium bicarbonate (5 mL) 2H), 2.18–2.11 (m, 2H), 1.52–1.26 (m, 12H), 0.91–0.86 (m, 6H). 13
C
and diluted with diethyl ether (20 mL). The ether solution was NMR (100 MHz, CDCl3) d (ppm): 148.7, 142.0, 141.5, 133.3, 132.6,
dried over MgSO4 and concentrated under reduced pressure. The 129.2, 127.3, 108.6, 96.0, 86.6, 33.0, 31.7, 31.6, 30.6, 28.9, 28.2, 22.5,
residue was purified by flash column chromatography on silica 22.1, 14.1, 13.8. MS (EI, 70 eV): m/z (%) = 358 (3.3) [M]+, 205 (15),
gel (light petroleum ether/diethyl ether, 3 : 1 or 10 : 1).
149 (100), 77 (63), 57 (56). Anal. calcd for C22H30O2S: C, 73.70; H,
(1E,5E)-1-Phenylsulfonyl-2-butyl-1,5-decadien-3-yne 4a [Table 3, 8.43. Found: C, 73.83; H, 8.19.
entry 1]. Oil. IR (neat): nmax/cmÀ1 2958, 2930, 2187, 1570, 1447,
(1E,5E)-1-Phenylsulfonyl-2-hexyl-8-methoxy-1,5-octadien-3-yne
1317, 1149, 1085, 958, 821, 752. 1H NMR (400 MHz, CDCl3) d 4f [Table 3, entry 6]. Oil. IR (neat): nmax/cmÀ1 2929, 2859, 2189,
(ppm): 7.91 (d, J = 7.2 Hz, 2H), 7.62–7.52 (m, 3H), 6.48 (s, 1H), 6.25 1571, 1447, 1316, 1149, 1085, 912, 821, 733. 1H NMR (400 MHz,
(dt, J = 16.0, 7.6 Hz, 1H), 5.58 (d, J = 16.0 Hz, 1H), 2.68 (t, J = 7.6 Hz, CDCl3) d (ppm): 7.91 (d, J = 7.6 Hz, 2H), 7.64–7.53 (m, 3H), 6.48
2H), 2.18–2.11 (m, 2H), 1.51–1.25 (m, 8H), 0.92–0.87 (m, 6H). 13C (s, 1H), 6.24 (dt, J = 16.0, 7.6 Hz, 1H), 5.68 (d, J = 16.0 Hz, 1H),
NMR (100 MHz, CDCl3) d (ppm): 148.6, 142.1, 141.4, 133.3, 132.7, 3.44 (t, J = 6.8 Hz, 2H), 3.33 (s, 3H), 2.67 (t, J = 7.6 Hz, 2H), 2.44–
129.2, 127.3, 108.6, 95.9, 86.7, 33.0, 31.5, 30.6, 30.4, 22.4, 22.1, 13.9, 2.39 (m, 2H), 1.51–1.45 (m, 2H), 1.28–1.24 (m, 6H), 0.88 (t, J =
13.8. MS (EI, 70 eV): m/z (%) = 330 (13) [M]+, 288 (25), 205 (70), 163 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) d (ppm): 144.6, 142.0,
(64), 91 (83), 77 (100), 57 (65). Anal. calcd for C20H26O2S: C, 72.69; 141.3, 133.3, 132.9, 129.3, 127.3, 110.5, 95.4, 87.1, 71.1, 58.7, 33.6,
H, 7.93. Found: C, 72.78; H, 7.70.
31.6, 31.5, 28.9, 28.2, 22.5, 14.1. MS (EI, 70 eV): m/z (%) = 360 (2.3)
(1E,5E)-1-Phenylsulfonyl-2-butyl-6-phenyl-1,5-hexadien-3-yne [M]+, 277 (15), 125 (38), 77 (87), 57 (100). Anal. calcd for
4b [Table 3, entry 2]. Oil. IR (neat): nmax/cmÀ1 3031, 2930, 2180, C21H28O3S: C, 69.96; H, 7.83. Found: C, 70.13; H, 7.59.
1561, 1447, 1314, 1147, 1085, 954, 819, 749. 1H NMR (400 MHz,
(1E,5E)-1-Phenylsulfonyl-2-phenyl-8-methoxy-1,5-octadien-3-
CDCl3) d (ppm): 7.93 (d, J = 7.2 Hz, 2H), 7.63–7.53 (m, 3H), 7.41– yne 4g [Table 3, entry 7]. Oil. IR (neat): nmax/cmÀ1 2928, 2189,
7.31 (m, 5H), 7.01 (d, J = 16.0 Hz, 1H), 6.55 (s, 1H), 6.26 (d, J = 1557, 1447, 1306, 1149, 1084, 909, 824, 733. 1H NMR (400 MHz,
16.0 Hz, 1H), 2.73 (t, J = 7.6 Hz, 2H), 1.56–1.51 (m, 2H), 1.39–1.33 CDCl3) d (ppm): 7.61–7.59 (m, 2H), 7.52–7.48 (m, 1H), 7.39–
(m, 2H), 0.92 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) d 7.28 (m, 7H), 6.83 (s, 1H), 6.26 (dt, J = 16.0, 7.6 Hz, 1H), 5.68
(ppm): 144.2, 141.9, 141.0, 135.6, 133.4, 133.1, 129.4, 129.3, (d, J = 16.0 Hz, 1H), 3.42 (t, J = 6.8 Hz, 2H), 3.32 (s, 3H), 2.43–
128.9, 127.4, 126.6, 106.7, 96.2, 90.2, 31.4, 30.5, 22.4, 13.9. MS 2.38 (m, 2H). 13C NMR (100 MHz, CDCl3) d (ppm): 145.1,
(EI, 70 eV): m/z (%) = 350 (66) [M]+, 219 (96), 209 (72), 165 (100), 141.0, 137.7, 134.8, 134.2, 133.2, 129.5, 128.9, 128.8, 127.9,
152 (74), 115 (65), 77 (46). Anal. calcd for C22H22O2S: C, 75.41; H, 127.7, 110.5, 96.7, 87.5, 71.1, 58.7, 33.6. MS (EI, 70 eV):
6.33. Found: C, 75.17; H, 6.56.
m/z (%) = 352 (1.8) [M]+, 277 (54), 178 (61), 105 (66), 84 (100),
(1E,5E)-1-Phenylsulfonyl-2,6-diphenyl-1,5-hexadien-3-yne 4c 77 (69). Anal. calcd for C21H20O3S: C, 71.56; H, 5.72. Found: C,
[Table 3, entry 3]. Oil. IR (neat): nmax/cmÀ1 3060, 2926, 2180, 71.29; H, 5.54.
1557, 1447, 1307, 1147, 1084, 956, 819, 751. 1H NMR (400 MHz,
(1E,5E)-1-(Ethoxycarbonyl)-2-butyl-6-phenyl-1,5-hexadien-3-
CDCl3) d (ppm): 7.63 (d, J = 7.2 Hz, 2H), 7.52 (t, J = 7.4 Hz, 1H), yne 4h [Table 3, entry 8]. Oil. IR (neat): nmax/cmÀ1 2959, 2931,
7.43–7.30 (m, 12H), 7.02 (d, J = 16.4 Hz, 1H), 6.90 (s, 1H), 6.26 2180, 1709, 1595, 1448, 1159, 909, 733. 1H NMR (400 MHz,
(d, J = 16.4 Hz, 1H). 13C NMR (100 MHz, CDCl3) d (ppm): 144.5, CDCl3) d (ppm): 7.43–7.31 (m, 5H), 7.02 (d, J = 16.0 Hz, 1H), 6.32
140.9, 137.6, 135.5, 134.9, 134.2, 133.2, 129.6, 129.5, 129.0, (d, J = 16.0 Hz, 1H), 6.08 (s, 1H), 4.19 (q, J = 7.2 Hz, 2H), 2.80
128.9, 128.8, 128.0, 127.7, 126.7, 106.6, 97.5, 90.5. MS (EI, (t, J = 7.6 Hz, 2H), 1.63–1.57 (m, 2H), 1.43–1.38 (m, 2H), 1.29
70 eV): m/z (%) = 370 (8.3) [M]+, 305 (25), 229 (100), 215 (40), (t, J = 7.2 Hz, 3H), 0.95 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz,
77 (54). Anal. calcd for C24H18O2S: C, 77.81; H, 4.90. Found: C, CDCl3) d (ppm): 165.9, 143.2, 143.0, 136.0, 129.1, 128.8, 126.5,
77.54; H, 4.62.
123.7, 107.5, 93.8, 92.8, 60.0, 32.1, 30.8, 22.5, 14.3, 14.0. MS
(1E,5E)-1-Phenylsulfonyl-2-hexyl-6-phenyl-1,5-hexadien-3-yne (EI, 70 eV): m/z (%) = 282 (45) [M]+, 253 (85), 211 (100), 165 (78),
4d [Table 3, entry 4]. Oil. IR (neat): nmax/cmÀ1 3032, 2929, 2858, 115 (57). Anal. calcd for C19H22O2: C, 80.81; H, 7.85. Found: C,
2181, 1567, 1447, 1314, 1148, 1085, 954, 819, 749. 1H NMR 80.53; H, 7.62.
2690 | New J. Chem., 2014, 38, 2686--2692
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(1E,5E)-1-(Ethoxycarbonyl)-2-butyl-1,5-dodecadien-3-yne 4i
(1E,5E)-1-(Ethoxycarbonyl)-2-butyl-8-methoxy-1,5-octadien-3-
[Table 3, entry 9]. Oil. IR (neat): nmax/cmÀ1 2959, 2930, 2188, yne 4n [Table 3, entry 14]. Oil. IR (neat): nmax/cmÀ1 2959, 2930,
1
1714, 1601, 1466, 1159, 909, 735. H NMR (400 MHz, CDCl3) d 2189, 1713, 1602, 1465, 1159, 1120, 911, 733. 1H NMR
(ppm): 6.24 (dt, J = 16.0, 7.2 Hz, 1H), 6.01 (s, 1H), 5.63 (d, J = (400 MHz, CDCl3) d (ppm): 6.24 (dt, J = 16.0, 7.2 Hz, 1H), 6.01
16.0 Hz, 1H), 4.16 (q, J = 7.2 Hz, 2H), 2.75 (t, J = 7.6 Hz, 2H), (s, 1H), 5.72 (d, J = 16.0 Hz, 1H), 4.16 (q, J = 7.2 Hz, 2H), 3.46
2.18–2.11 (m, 2H), 1.58–1.25 (m, 15H), 0.95–0.91 (m, 6H). 13C (t, J = 6.6 Hz, 2H), 3.35 (s, 3H), 2.75 (t, J = 7.6 Hz, 2H), 2.46–2.41
NMR (100 MHz, CDCl3) d (ppm): 166.0, 147.2, 143.5, 123.1, (m, 2H), 1.58–1.51 (m, 2H), 1.41–1.33 (m, 2H), 1.28 (t, J = 7.2 Hz,
109.2, 93.5, 89.1, 59.9, 33.3, 32.1, 31.6, 30.7, 28.8, 28.6, 22.6, 3H), 0.92 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) d (ppm):
22.4, 14.2, 14.1, 13.9. MS (EI, 70 eV): m/z (%) = 290 (17) [M]+, 261 165.9, 143.3, 143.1, 123.4, 111.1, 93.0, 89.6, 71.3, 59.9, 58.7,
(48), 233 (47), 179 (52), 163 (100), 91 (73), 57 (59). Anal. calcd for 33.6, 32.1, 30.7, 22.4, 14.3, 13.9. MS (EI, 70 eV): m/z (%) = 264
C
19H30O2: C, 78.57; H, 10.41. Found: C, 78.71; H, 10.29.
(1E,5E)-1-(Ethoxycarbonyl)-2,6-diphenyl-1,5-hexadien-3-yne 4j C16H24O3: C, 72.69; H, 9.15. Found: C, 72.83; H, 8.96.
(27) [M]+, 235 (100), 219 (93), 161 (70), 91 (48). Anal. calcd for
[Table 3, entry 10]. Oil. IR (neat): nmax/cmÀ1 3059, 3030, 2981,
2928, 2181, 1717, 1589, 1447, 1163, 909, 733. 1H NMR
(400 MHz, CDCl3) d (ppm): 7.46–7.28 (m, 10H), 7.03 (d, J =
16.0 Hz, 1H), 6.34–6.30 (m, 2H), 4.09 (q, J = 7.2 Hz, 2H), 1.14
(t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) d (ppm): 165.4,
143.7, 143.4, 138.5, 136.7, 135.9, 129.2, 128.8, 128.4, 127.9,
126.6, 124.4, 107.4, 95.2, 92.4, 60.4, 14.0. MS (EI, 70 eV): m/z
(%) = 302 (14) [M]+, 273 (55), 115 (37), 105 (100), 77 (59), 71 (76),
57 (96). Anal. calcd for C21H18O2: C, 83.42; H, 6.00. Found: C,
83.19; H, 5.78.
(1E,5E)-1-(Ethoxycarbonyl)-2-phenyl-1,5-dodecadien-3-yne 4k
[Table 3, entry 11]. Oil. IR (neat): nmax/cmÀ1 2958, 2928, 2188,
1717, 1592, 1445, 1257, 1162, 910, 733. 1H NMR (400 MHz,
CDCl3) d (ppm): 7.42–7.40 (m, 2H), 7.36–7.33 (m, 3H), 6.29–6.22
(m, 2H), 5.64 (d, J = 16.0 Hz, 1H), 4.06 (q, J = 7.2 Hz, 2H), 2.16–
2.11 (m, 2H), 1.42–1.24 (m, 8H), 1.13 (t, J = 7.2 Hz, 3H), 0.88
(t, J = 6.6 Hz, 3H). 13C NMR (100 MHz, CDCl3) d (ppm): 165.4,
147.8, 138.8, 136.8, 128.7, 128.4, 127.8, 124.0, 109.1, 94.9, 88.9,
60.3, 33.4, 31.6, 28.8, 28.5, 22.6, 14.1, 14.0. MS (EI, 70 eV):
m/z (%) = 310 (26) [M]+, 265 (39), 211 (51), 185 (52), 165 (100),
57 (52). Anal. calcd for C21H26O2: C, 81.25; H, 8.44. Found: C,
81.03; H, 8.19.
(1E,5E)-1-(Ethoxycarbonyl)-2-cyclopropyl-6-phenyl-1,5-hexadien-
3-yne 4l [Table 3, entry 12]. Oil. IR (neat): nmax/cmÀ1 2982, 2935,
2183, 1705, 1587, 1448, 1159, 1038, 911, 734. 1H NMR (400 MHz,
CDCl3) d (ppm): 7.42–7.29 (m, 5H), 6.97 (d, J = 16.0 Hz, 1H), 6.25
(d, J = 16.0 Hz, 1H), 6.10 (s, 1H), 4.20 (q, J = 7.2 Hz, 2H), 3.25–3.22
(m, 1H), 1.30 (t, J = 7.2 Hz, 3H), 0.98–0.93 (m, 4H). 13C NMR
(100 MHz, CDCl3) d (ppm): 166.6, 146.4, 143.3, 135.8, 129.1, 128.8,
126.6, 122.4, 107.1, 93.6, 88.2, 59.9, 14.3, 12.5, 8.6. MS (EI, 70 eV):
m/z (%) = 266 (27) [M]+, 237 (100), 191 (46), 165 (61), 105 (81), 77
(83). Anal. calcd for C18H18O2: C, 81.17; H, 6.81. Found: C, 80.89;
H, 6.65.
(1E,5E)-1-(Ethoxycarbonyl)-2-cyclopropyl-1,5-decadien-3-yne 4m
[Table 3, entry 13]. Oil. IR (neat): nmax/cmÀ1 2959, 2931,
2190, 1709, 1591, 1266, 1158, 1038, 922, 858. 1H NMR
(400 MHz, CDCl3) d (ppm): 6.10 (dt, J = 16.0, 7.6 Hz, 1H), 5.93
(s, 1H), 5.46 (d, J = 16.0 Hz, 1H), 4.07 (q, J = 7.2 Hz, 2H), 3.13–
3.05 (m, 1H), 2.07–2.00 (m, 2H), 1.32–1.14 (m, 7H), 0.83–0.76
(m, 7H). 13C NMR (100 MHz, CDCl3) d (ppm): 166.7, 147.5,
146.7, 121.9, 108.8, 93.3, 84.4, 59.8, 32.9, 30.6, 22.1, 14.3, 13.8,
12.4, 8.5. MS (EI, 70 eV): m/z (%) = 246 (14) [M]+, 217 (55), 147
(54), 128 (97), 91 (100). Anal. calcd for C16H22O2: C, 78.01; H,
9.00. Found: C, 77.76; H, 9.15.
Acknowledgements
We thank the National Natural Science Foundation of China
(No. 20862008) and Key Laboratory of Functional Small Organic
Molecule, Ministry of Education (No. KLFS-KF-201213) for
financial support.
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