Highly regio-and stereoselective synthesis of (1Z,3E)-2-sulfonyl-3-stannyl- 1,3-dienes by hydrostannylation of (Z)-2-sulfonyl-1,3-enynes

Article abstract of DOI:10.3184/174751913X13816588007726

The Stille coupling of (E)-α-stannylvinyl sulfones with alkynyl bromides in DMF in the presence of Pd(PPh3)4 and CuI gave (Z)-2-sulfonyl-1,3- enynes in good yields. (Z)-2-Sulfonyl-1,3-enynes underwent palladium-catalysed hydrostannylation with tributyltin hydride to afford highly regio-and stereoselectively (1Z,3E)-2-sulfonyl-3-stannyl-1,3-dienes.

Full text of DOI:10.3184/174751913X13816588007726

JOURNAL OF CHEMICAL RESEARCH 2013
NOVEMBER, 701–704
RESEARCH PAPER 701
Highly regio- and stereoselective synthesis of (1Z,3E)-2-sulfonyl-3-stannyl-
1,3-dienes by hydrostannylation of (Z)-2-sulfonyl-1,3-enynes
Shiyun Xiea, Ji Xub, Tao Yana and Mingzhong Caia*
aDepartment of Chemistry, Jiangxi Normal University, Nanchang 330022, P.R. China
bShenzhen Second People’s Hospital and The First Affiliated Hospital of Shenzhen University, Shenzhen 518060, P.R. China
The Stille coupling of (E)-α-stannylvinyl sulfones with alkynyl bromides in DMF in the presence of Pd(PPh ) and CuI gave (Z)-2-
sulfonyl-1,3-enynes in good yields. (Z)-2-Sulfonyl-1,3-enynes underwent palladium-catalysed hydrostann3yl4ation with tributyltin
hydride to afford highly regio- and stereoselectively (1Z,3E)-2-sulfonyl-3-stannyl-1,3-dienes.
Keywords: difunctionalised 1,3-diene, hydrostannylation, (E)-α-stannylvinyl sulfone, stereoselective synthesis
Table 1 Synthesis of (Z)-2-sulfonyl-substituted 1,3-enynes 3a–ha
The stereocontrolled synthesis of 1,3-dienes containing metal
R1
Product
Yield/%b
or heteroatom functional groups has received much attention
in organic synthesis because many useful functional group
transformations can be achieved by introduction and removal of
metal or heteroatom functions. The stereoselective synthesis of
1,3-dienylsulfides,1–3 1,3-dienylselenides,4–6 1,3-dienylsilanes7–9
and 1,3-dienylstannanes10–12 has already been described in the
literature. Recently, the synthesis of difunctionalised 1,3-dienes
has also attracted great interest in organic synthesis since
such dienes may find use as synthetic building blocks.13–18 In
addition, difunctionalised 1,3-dienes containing a heteroatom
can control reactions both regio- and stereoselectivity and play
a very important role in cycloadditions.19–22 Jin and co-workers
reported the stereoselective synthesis of 2-alkoxy-3-alkyl(aryl)
thiobuta-1,3-dienes by a Negishi coupling reaction between
an α-alkyl(aryl)thio vinyl zinc chloride and α-bromo vinyl
ether.23 Coleman and Walczak reported the stereoselective
synthesis of (E,E)-1-tributylstannyl-4-borylbuta-1,3-diene and
its use as an orthogonal Stille and Suzuki–Miyaura coupling
partner.24 Recently, we have described the stereoselective
synthesis of (Z,Z)-2-silyl-3-stannyl-substituted 1,3-dienes
by the hydromagnesiation of alkynylsilanes, followed by the
cross-coupling reaction with (E)-α-iodovinylstannanes in the
presence of Pd(PPh3)4 catalyst.25 However, to the best of our
knowledge, no well-established method is used to prepare
stereoselectively (1Z,3E)-2-sulfonyl-3-stannyl-1,3-dienes. Here
we report that (1Z,3E)-2-sulfonyl-3-stannyl-1,3-dienes can be
conveniently obtained by Stille coupling of (E)-α-stannylvinyl
sulfones with alkynyl bromides, followed by hydrostannylation
with tributyltin hydride in the presence of Pd(PPh3)4.
The starting (E)-α-stannylvinyl sulfones were easily prepared
by the palladium-catalysed hydrostannylation of alkynyl
sulfones according to the procedure reported by us previously.26
(E)-α-Stannylvinyl sulfones 1 are difunctional group reagents
in which two synthetically versatile groups are linked to the
same olefinic carbon atom and can be considered both as
vinylstannanes and as vinyl sulfones. With a convenient route
to the (E)-α-stannylvinyl sulfones 1, we decided to establish the
feasibility of using 1 in cross-coupling reactions with alkynyl
bromides 2. Gratifyingly, when the cross-coupling reactions
of 1 with a variety of alkynyl bromides 2 were conducted in
DMF at room temperature using Pd(PPh3)4 and CuI as co-
Entry
R
1
2
3
4
5
6
7
8
n-C4H9
n-C4H9
n-C4H9
n-C4H9
Ph
CH3OCH2CH2
CH3OCH2CH2
CH3OCH2CH2
n-C6H13
Ph
CH3OCH2CH2
Cyclopropyl
n-C6H13
n-C6H13
Ph
CH3OCH2CH2
3a
3b
3c
3d
3e
3f
81
78
80
67
78
71
76
74
3g
3h
aReaction was performed with (E)-α-stannylvinyl sulfone 1 (1 mmol),
alkynyl bromide 2 (1.1 mmol), Pd(PPh3)4 (0.05 mmol), CuI (0.75 mmol) in
DMF (8 mL) at room temperature under Ar.
bIsolated yield based on the (E)-α-stannylvinyl sulfone 1 used.
catalyst (Scheme 1), fairly rapid reactions occurred affording
stereoselectively the desired (Z)-2-sulfonyl-1,3-enynes 3 in
good yields. The experimental results are summarised in
Table 1.
It is well documented that the cross-coupling reaction
(Stille coupling) of vinyl-stannanes with organic halides in
the presence of a palladium catalyst occurs with retention
of configuration.27,28 In addition, the Z-configuration of the
1
compound 3c was confirmed by the NOESY in the H NMR
spectrum. An enhancement of the allylic protons was observed
as the vinylic proton (δ=6.49) of 3c was irradiated. A correlation
between the allylic protons (δ=2.81–2.76) and aromatic protons
(δ=7.96) was observed. The NOE results indicate that 3c has
the expected Z-configuration and the cross-coupling reaction
of (E)-α-stannylvinyl sulfones 1 with alkynyl bromides 2
occurs with the retention of the configuration of the starting
compounds 1.
Palladium-catalysed hydrostannylation of alkynes provides
a simple, general route for the synthesis of vinylstannanes.29
The palladium-catalysed hydrostannylation of substituted
enynes generally leads to the α-addition product, providing
a convenient route for the synthesis of 1,3-dienylstannanes.
The Pd-catalysed hydrostannylation of 1-methoxycarbonyl-
substituted enynes,30 chloroenynes and alkyl-substituted
enynes,31 enediynes,32 eneynols33 has been reported. In order
to prepare highly regio- and stereoselectively (1Z,3E)-2-
sulfonyl-3-stannyl-substituted 1,3-dienes, we investigated
R
SO2Ph
R
H
SO2Ph
SnBu3
(
)
CuI
/
Pd PPh3 4
R1
+
r
B
H
DMF, rt, 24 h
R1
3
1
2
Scheme 1
* Correspondent. E-mail: caimzhong@163.com
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702 JOURNAL OF CHEMICAL RESEARCH 2013
R
R
SO2Ph
SO2Ph
R1
H
Pd(PPh3)4
+
HSnBu3
H
H
THF, rt, 2 h
R1
SnBu3
4
3
Scheme 2
the palladium-catalysed hydrostannylation of (Z)-2-sulfonyl-
substituted 1,3-enynes 3 with tributyltin hydride (Scheme 2).
Our initial efforts were devoted to the selection of an efficient
catalyst and a suitable solvent for an efficient hydrostannylation
reaction of (Z)-2-sulfonyl-substituted 1,3-enynes 3 with
Bu3SnH. The reaction of (Z)-6-phenylsulfonyltetradec-5-en-
7-yne 3a(1 mmol) and Bu3SnH (1.1 mmol) was chosen as the
model reaction. The influences of the catalysts and solvents
on the reaction were examined, and the results are listed in
Table 2. This shows that for the palladium catalysts evaluated
[Pd(OAc)2, Pd(PPh3)4, PdCl2(PPh3)2, and PdCl2], Pd(OAc)2 and
PdCl2 were inefficient, and Pd(PPh3)4 proved to be the most
efficient. Both THF and benzene could be used as solvent, but
THF was the best choice. Increasing the amount of Pd(PPh3)4
could shorten the reaction time, but did not increase the yield
to afford regio- and stereoselectively the desired (1Z,3E)-2-
sulfonyl-3-stannyl-substituted 1,3-dienes 4 in good yields. In
all cases, a single regio- and geometric isomer was formed
according to Scheme 2 and the isolation of products only
involved direct flash chromatography.
The regioselectivity is easily assessed by the appropriate
coupling patterns of the vinylic proton. One olefinic proton
signalofcompounds4a, 4c, 4e, 4fand4hsplitscharacteristically
into one triplet at δ=5.60–5.77 with coupling constant J=6.8–
7.6 Hz, which indicated that the hydrostannylation to the
compounds 3 had taken place with strong preference for the
addition of the hydride at the more electron-deficient terminus
of the acetylene. A reasonable explanation lies in the electronic
polarisation of the acetylene due to the electron-withdrawing
nature of the sulfone moiety. The stereochemistry of the
1
of
(5Z,7E)-6-phenylsulfonyl-7-tributylstannyltetradeca-5,7-
addition was readily apparent from the H NMR spectra of
compounds 4 which showed a (3JSn117-H) coupling constant of
56–64 Hz, fully in accord with an E geometry and overall cis
addition of tin hydride.34
diene (4a). Taken together, a good result was obtained when
the hydrostannylation reaction was carried out with 2 mol%
Pd(PPh3)4 in THF at room temperature for 4 h under an argon
atmosphere (entry 5).
To examine the scope for this hydrostannylation reaction,
the hydrostannylation reactions of a variety of (Z)-2-sulfonyl-
substituted 1,3-enynes 3 with Bu3SnH were investigated under
the optimum conditions and the experimental results are listed
in Table 3. As shown in Table 3, the palladium-catalysed
hydrostannylation reactions of a variety of (Z)-2-sulfonyl-
substituted 1,3-enynes 3 with Bu3SnH proceeded smoothly in
the presence of 2 mol% Pd(PPh3)4 in THF at room temperature
In conclusion, we have developed a highly efficient method
for the stereoselective synthesis of (1Z,3E)-2-sulfonyl-3-
stannyl-substituted 1,3-dienes by Stille coupling of (E)-α-
stannylvinyl sulfones with alkynyl bromides, followed by the
palladium-catalysed hydrostannylation reaction with tributyltin
hydride. The present method has some attractive advantages of
readily available starting materials, mild reaction conditions,
high regio- and stereoselectivity and good yields.
Experimental
THF was distilled from sodium prior to use; all other reagents were
used as received without further purification. All reactions were
carried out under an atmosphere of Ar in oven-dried glassware with
magnetic stirring. 1H NMR spectra were recorded on a Bruker Avance
400 (400 MHz) spectrometer with TMS as an internal standard using
CDCl3 as the solvent. 13C NMR spectra were recorded on a Bruker
Avance 400 (100 MHz) spectrometer using CDCl3 as the solvent.
Microanalyses were obtained using a Perkin-Elmer 240 elemental
analyser.
Table 2 Influences of catalysts and solvents in the hydrostannylation
reactiona
Yield/%b
of 4a
Entry
Catalyst (mol%)
Solvent
Time/h
1
2
3
4
5
6
7
8
9
Pd(OAc)2 (2)
Pd(OAc)2 (2)
PdCl2(PPh3)2 (2)
PdCl2(PPh3)2 (2)
Pd(PPh3)4 (2)
Pd(PPh3)4 (2)
Pd(PPh3)4 (5)
PdCl2 (2)
THF
Benzene
THF
Benzene
THF
Benzene
THF
THF
24
24
8
8
4
8
2
24
24
0
0
57
49
85
69
84
0
Synthesis of (Z)-2-sulfonyl-substituted 1,3-enynes 3a–h; general
procedure
(E)-α-Stannylvinyl sulfone
1 (1.0 mmol) and alkynyl bromide
PdCl2 (2)
Benzene
0
2 (1.1 mmol) were dissolved in DMF (8 mL) under Ar at room
temperature. Pd(PPh3)4 (0.05 mmol) and CuI (0.75 mmol) were then
added. The mixture was stirred for 20–24 h at room temperature and
monitored by TLC (SiO2) for the disappearance of the starting (E)-
α-stannylvinyl sulfone 1. The reaction mixture was diluted with
diethyl ether (30 mL), filtered and then treated with 20% aqueous KF
(10 mL) for 30 min before being dried and concentrated. The residue
was purified by column chromatography on silica gel (eluent: light
petroleum ether/Et2O, 5:1).
(Z)-6-Phenylsulfonyltetradec-5-en-7-yne (3a): Colourless oil. IR (film):
ν (cm–1) 2957, 2933, 2873, 2238, 1712, 1448, 1330, 1155, 721, 688; 1H NMR
(CDCl3): δ 7.96–7.94 (m, 2H), 7.63–7.51 (m, 3H), 6.45 (t, J=7.6 Hz, 1H),
2.83–2.78 (m, 2H), 2.22 (t, J=7.6 Hz, 2H), 1.44–1.22 (m, 12H), 0.93–0.85
(m, 6H); 13C NMR (CDCl3): δ 150.5, 140.2, 133.6, 128.7, 128.3, 127.1, 95.5,
74.6, 31.2, 30.5, 29.2, 28.7, 28.3, 22.6, 22.4, 19.7, 13.9, 13.8; Anal. Calcd for
C20H28SO2: C, 72.29; H, 8.43. Found: C, 72.05; H, 8.22%.
aReaction was performed with 3a (1 mmol), Bu3SnH (1.1 mmol), solvent
(2 mL) at room temperature under Ar.
bIsolated yield.
Table 3 Synthesis of (1Z,3E)-2-sulfonyl-3-stannyl-substituted 1,3-dienes 4a
Entry
R
R1
Product
Yield/%b
1
2
3
4
5
6
7
8
n-C4H9
n-C4H9
n-C4H9
n-C4H9
Ph
CH3OCH2CH2
CH3OCH2CH2
CH3OCH2CH2
n-C6H13
Ph
CH3OCH2CH2
Cyclopropyl
n-C6H13
n-C6H13
Ph
CH3OCH2CH2
4a
4b
4c
4d
4e
4f
80
82
78
74
77
79
81
76
4g
4h
aReaction was performed with 3 (1 mmol), Bu3SnH (1.1 mmol), Pd(PPh3)4
(0.02 mmol), THF (2 mL) at room temperature under Ar for 4 h.
bIsolated yield.
(Z)-6-Phenylsulfonyl-8-phenyloct-5-en-7-yne (3b): Colourless oil.
IR (film): ν (cm–1) 2957, 2929, 2874, 2206, 1720, 1593, 1447, 1323, 1158,
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JOURNAL OF CHEMICAL RESEARCH 2013 703
1
756, 688; H NMR (CDCl3): δ 8.06–8.03 (m, 2H), 7.69–7.56 (m, 3H),
29.4, 29.3, 29.0, 28.9, 27.8, 27.4, 22.5, 22.4, 14.0, 13.9, 13.7, 11.2; Anal.
Calcd for C32H56SO2Sn: C, 61.64; H, 9.05. Found: C, 61.38; H, 8.87%.
(1E,3Z)-1-Phenyl-2-tributylstannyl-3-phenylsulfonylocta-1,3-
diene (4b): Colourless oil. IR (film): ν (cm–1) 3060, 2956, 2925, 2871,
1585, 1464, 1447, 1304, 1152, 1084, 727, 688; 1H NMR (CDCl3): δ 7.75
(d, J=8.0 Hz, 2H), 7.46–7.32 (m, 3H), 7.02–6.73 (m, 5H), 6.58 (s,
3JSn–H =64 Hz, 1H), 5.79 (t, J=7.2 Hz, 1H), 2.74–2.69 (m, 2H), 1.62–1.28
(m, 16H), 1.20–1.15 (m, 6H), 0.96–0.84 (m, 12H); 13C NMR (CDCl3):
δ 144.5, 143.5, 142.3, 141.3, 140.4, 136.6, 133.2, 128.7, 128.2, 128.1,
127.8, 127.1, 31.3, 29.0, 28.1, 27.5, 22.4, 13.9, 13.8, 11.6; Anal. Calcd for
C32H48SO2Sn: C, 62.44; H, 7.86. Found: C, 62.17; H, 7.59%.
7.36–7.28 (m, 5H), 6.66 (t, J=7.6 Hz, 1H), 2.93–2.87 (m, 2H), 1.54–1.32
(m, 4H), 0.98 (t, J=7.2 Hz, 3H); 13C NMR (CDCl3): δ 151.5, 140.2, 133.6,
131.5, 128.9, 128.6, 128.4, 128.3, 127.4, 122.0, 93.5, 83.4, 31.1, 28.5, 22.4,
13.9; Anal. Calcd for C20H20SO2: C, 74.08; H, 6.17. Found: C, 73.90; H,
5.93%.
(Z)-6-Phenylsulfonyl-10-methoxydec-5-en-7-yne (3c): Colourless oil.
IR (film): ν (cm–1) 2952, 2922, 2875, 2219, 1586, 1447, 1315, 1149, 1119,
1083, 730, 688; 1H NMR (CDCl3): δ 7.96 (d, J=8.4 Hz, 2H), 7.63–7.52 (m,
3H), 6.49 (t, J=7.4 Hz, 1H), 3.40 (t, J=6.8 Hz, 2H), 3.33 (s, 3H), 2.81–2.76
(m, 2H), 2.52 (t, J=6.8 Hz, 2H), 1.45–1.32 (m, 4H), 0.91 (t, J=6.8 Hz,
3H); 13C NMR (CDCl3): δ 150.4, 140.3, 133.6, 128.8, 128.2, 127.1, 95.8,
75.1, 70.4, 58.6, 31.2, 30.5, 28.6, 22.4, 13.9; Anal. Calcd for C17H22SO3: C,
66.63; H, 7.24. Found: C, 66.35; H, 6.97%.
(Z)-6-Phenylsulfonyl-8-cyclopropyloct-5-en-7-yne (3d): Colourless
oil. IR (film): ν (cm–1) 2952, 2931, 2876, 2215, 1595, 1448, 1324, 1157, 757,
689; 1H NMR (CDCl3): δ 7.95–7.93 (m, 2H), 7.63–7.53 (m, 3H), 6.28 (t,
J=7.4 Hz, 1H), 2.68–2.64 (m, 2H), 1.67–1.60 (m, 1H), 1.53–1.28 (m, 4H),
0.96–0.88 (m, 7H); 13C NMR (CDCl3): δ 151.0, 140.3, 133.7, 128.7, 128.3,
127.1, 94.6, 76.8, 31.1, 28.4, 22.5, 14.0, 9.8, 0.1; Anal. Calcd for C17H20SO2:
C, 70.80; H, 6.99. Found: C, 70.55; H, 6.72%.
(Z)-1-Phenyl-2-phenylsulfonyldec-1-en-3-yne (3e): Colourless oil. IR
(film): ν (cm–1) 3065, 2958, 2927, 2878, 2216, 1589, 1446, 1322, 1149, 752,
689; 1H NMR (CDCl3): δ 7.97–7.92 (m, 4H), 7.86 (s, 1H), 7.63–7.34 (m,
6H), 2.21 (t, J=7.2 Hz, 2H), 1.66–1.54 (m, 2H), 1.38–1.24 (m, 6H), 0.92
(t, J=7.2 Hz, 3H); 13C NMR (CDCl3): δ 140.7, 139.2, 133.5, 133.1, 131.1,
130.1, 128.9, 128.8, 128.6, 124.8, 105.2, 73.2, 30.8, 29.5, 28.4, 22.7, 19.8,
14.0; Anal. Calcd for C22H24SO2: C, 74.96; H, 6.81. Found: C, 74.68; H,
6.67%.
(3E,5Z)-1-Methoxy-4-tributylstannyl-5-phenylsulfonyldeca-3,5-diene
(4c): Colourless oil. IR (film): ν (cm–1) 3067, 2956, 2924, 2871, 1587,
1464, 1447, 1305, 1153, 1119, 1085, 728, 688; 1H NMR (CDCl3): δ 7.81
3
(d, J=7.2 Hz, 2H), 7.57–7.46 (m, 3H), 5.66 (t, J=6.8 Hz, JSn–H =56 Hz,
1H), 5.64 (t, J=7.6 Hz, 1H), 3.18 (s, 3H), 2.95 (t, J=6.8 Hz, 2H), 2.81–2.76
(m, 2H), 1.78–1.71 (m, 2H), 1.57–1.25 (m, 16H), 1.01–0.88 (m, 18H); 13
C
NMR (CDCl3): δ 143.2, 142.9, 141.7, 140.7, 140.5, 133.0, 128.8, 128.1,
71.8, 58.5, 31.9, 29.8, 29.0, 27.8, 27.4, 22.5, 13.9, 13.8, 11.2; Anal. Calcd
for C29H50SO3Sn: C, 58.30; H, 8.44. Found: C, 58.07; H, 8.21%.
(1E,3Z)-1-Cyclopropyl-2-tributylstannyl-3-phenylsulfonylocta-
1,3-diene (4d): Colourless oil. IR (film): ν (cm–1) 2957, 2924, 2872,
1587, 1464, 1447, 1304, 1152, 1083, 728, 688; 1H NMR (CDCl3): δ 7.86
(d, J=7.2 Hz, 2H), 7.55–7.44 (m, 3H), 5.78 (t, J=7.2 Hz, 1H), 4.88 (d,
3
J=9.6 Hz, JSn–H =56 Hz, 1H), 2.81–2.75 (m, 2H), 1.65–1.23 (m, 23H),
1.03–0.86 (m, 16H); 13C NMR (CDCl3): δ 151.5, 142.7, 141.2, 140.5, 137.6,
132.8, 128.6, 128.3, 31.9, 29.0, 27.9, 26.9, 22.5, 17.5, 13.8, 13.6, 11.1, 7.2;
Anal. Calcd for C29H48SO2Sn: C, 60.11; H, 8.35. Found: C, 59.87; H,
8.09%.
(1Z,3E)-1-Phenyl-2-phenylsulfonyl-3-tributylstannyldeca-1,3-
diene (4e): Colourless oil. IR (film): ν (cm–1) 3063, 2955, 2923, 2854,
1586, 1464, 1447, 1306, 1148, 1086, 750, 689; 1H NMR (CDCl3): δ 7.87
(d, J=7.6 Hz, 2H), 7.56–7.28 (m, 8H), 6.64 (s, 1H), 5.77 (t, J=7.0 Hz,
3JSn–H =56 Hz, 1H), 1.84–1.74 (m, 2H), 1.65–0.85 (m, 38H); 13C NMR
(CDCl3): δ 150.2, 148.4, 145.2, 135.1, 134.5, 133.0, 132.8, 130.0, 129.1,
128.6, 128.4, 127.7, 31.7, 29.7, 29.3, 29.1, 29.0, 27.5, 22.6, 14.0, 13.7, 11.3;
Anal. Calcd for C34H52SO2Sn: C, 63.46; H, 8.15. Found: C, 63.21; H,
7.87%.
(Z)-1-Methoxy-4-phenylsulfonyldodec-3-en-5-yne (3f): Colourless oil.
IR (film): ν (cm–1) 3056, 2959, 2930, 2875, 2211, 1584, 1449, 1320, 1149,
1089, 751, 687; 1H NMR (CDCl3): δ 7.97–7.94 (m, 2H), 7.65–7.51 (m, 3H),
6.56 (t, J=7.6 Hz, 1H), 3.50 (t, J=6.0 Hz, 2H), 3.34 (s, 3H), 3.11–3.06 (m,
2H), 2.22 (t, J=7.2 Hz, 2H), 1.42–1.20 (m, 8H), 0.91 (t, J=7.2 Hz, 3H); 13C
NMR (CDCl3): δ 150.7, 140.1, 133.8, 128.6, 128.3, 127.2, 96.3, 74.4, 70.8,
58.7, 32.1, 31.5, 29.1, 28.4, 22.6, 19.6, 14.0; Anal. Calcd for C19H26SO3: C,
68.23; H, 7.84. Found: C, 67.96; H, 7.62%.
(Z)-1-Methoxy-4-phenylsulfonyl-6-phenylhex-3-en-5-yne
(3g):
Colourless oil. IR (film): ν (cm–1) 3053, 2955, 2928, 2876, 2208, 1586,
1446, 1324, 1147, 1085, 756, 689; 1H NMR (CDCl3): δ 8.03 (d, J=7.2 Hz,
2H), 7.66–7.55 (m, 3H), 7.30–7.24 (m, 5H), 6.75 (t, J=7.6 Hz, 1H), 3.56
(t, J=6.0 Hz, 2H), 3.37 (s, 3H), 3.23–3.15 (m, 2H); 13C NMR (CDCl3): δ
151.7, 140.3, 133.8, 131.4, 129.0, 128.7, 128.5, 128.4, 127.6, 122.2, 93.3,
83.7, 70.6, 58.5, 31.9; Anal. Calcd for C19H18SO3: C, 69.91; H, 5.56. Found:
C, 69.67; H, 5.73%.
(3Z,5E)-1-Methoxy-4-phenylsulfonyl-5-tributylstannyldodeca-3,5-
diene (4f): Colourless oil. IR (film): ν (cm–1) 3067, 2956, 2923, 2852,
1587, 1464, 1447, 1316, 1150, 1119, 1082, 730, 688; 1H NMR (CDCl3): δ
7.82 (d, J=8.0 Hz, 2H), 7.56–7.44 (m, 3H), 5.71 (t, J=7.6 Hz, 1H), 5.63
3
(t, J=7.2 Hz, JSn–H =56 Hz, 1H), 3.51 (t, J=6.4 Hz, 2H), 3.34 (s, 3H),
3.11–3.06 (m, 2H), 1.64–1.58 (m, 2H), 1.56–0.83 (m, 38H); 13C NMR
(CDCl3): δ 148.5, 143.2, 140.4, 139.8, 136.5, 133.0, 128.7, 128.3, 71.9, 58.5,
31.6, 29.4, 29.3, 29.1, 29.0, 28.5, 27.4, 22.6, 14.1, 13.8, 11.2; Anal. Calcd for
C31H54SO3Sn: C, 59.52; H, 8.70. Found: C, 59.26; H, 8.55%.
(Z)-1,8-Dimethoxy-4-phenylsulfonyloct-3-en-5-yne (3h): Colourless
oil. IR (film): ν (cm–1) 3058, 2954, 2929, 2873, 2178, 1594, 1449, 1327,
(1E,3Z)-1-Phenyl-2-tributylstannyl-3-phenylsulfonyl-6-methoxyhexa-
1,3-diene (4g): Colourless oil. IR (film): ν (cm–1) 3060, 2956, 2924,
2871, 1585, 1464, 1447, 1316, 1305, 1149, 1118, 1082, 729, 687; 1H NMR
(CDCl3): δ 7.72 (d, J=7.6 Hz, 2H), 7.41–7.28 (m, 3H), 7.02–6.79 (m, 5H),
6.56 (s, 3JSn–H =64 Hz, 1H), 5.91 (t, J=7.2 Hz, 1H), 3.44 (t, J=6.4 Hz, 2H),
3.30 (s, 3H), 3.08–3.00 (m, 2H), 1.62–1.54 (m, 6H), 1.42–1.25 (m, 6H),
1.13–1.05 (m, 6H), 0.93 (t, J=7.2 Hz, 9H); 13C NMR (CDCl3): δ 144.2,
143.7, 143.4, 139.9, 137.5, 136.6, 133.2, 128.6, 128.4, 128.3, 127.7, 127.1,
71.5, 58.5, 29.0, 28.7, 27.5, 13.8, 11.6; Anal. Calcd for C31H46SO3Sn: C,
60.30; H, 7.51. Found: C, 60.48; H, 7.32%.
(3Z,5E)-1,8-Dimethoxy-4-phenylsulfonyl-5-tributylstannylocta-3,5-
diene (4h): Colourless oil. IR (film): ν (cm–1) 3066, 2922, 2873, 1586,
1463, 1447, 1316, 1188, 1149, 1118, 1083, 730, 688; 1H NMR (CDCl3): δ
7.82 (d, J=7.6 Hz, 2H), 7.58–7.46 (m, 3H), 5.74 (t, J=7.2 Hz, 1H), 5.68 (t,
J=7.2 Hz, 3JSn–H =56 Hz, 1H), 3.51 (t, J=6.2 Hz, 2H), 3.34 (s, 3H), 3.17
(s, 3H), 3.12–3.06 (m, 2H), 2.93 (t, J=7.0 Hz, 2H), 1.68–1.60 (m, 2H),
1.57–1.48 (m, 6H), 1.38–1.27 (m, 6H), 0.99 (t, J=8.0 Hz, 6H), 0.89 (t,
J=7.2 Hz, 9H); 13C NMR (CDCl3): δ 143.6, 143.0, 142.6, 140.3, 136.7,
133.1, 128.7, 128.3, 71.9, 71.8, 58.5, 58.4, 29.7, 29.0, 28.5, 27.4, 13.8, 11.2;
Anal. Calcd for C28H48SO4Sn: C, 56.10; H, 8.07. Found: C, 55.84; H,
7.79%.
1
1145, 1088, 752, 685; H NMR (CDCl3): δ 7.96 (d, J=7.2 Hz, 2H),
7.64–7.52 (m, 3H), 6.60 (t, J=7.6 Hz, 1H), 3.49 (t, J=6.0 Hz, 2H), 3.40
(t, J=7.0 Hz, 2H), 3.34 (s, 3H), 3.32 (s, 3H), 3.14–3.10 (m, 2H), 2.51 (t,
J=7.0 Hz, 2H); 13C NMR (CDCl3): δ 150.2, 140.1, 133.7, 128.9, 128.2,
127.3, 95.2, 74.9, 71.8, 70.6, 58.8, 58.4, 30.5, 29.6; Anal. Calcd for
C16H20SO4: C, 62.31; H, 6.54. Found: C, 62.52; H, 6.31%.
Synthesis of (1Z,3E)-2-sulfonyl-3-stannyl-substituted 1,3-dienes 4a–h;
general procedure
(Z)-2-Sulfonyl-substituted 1,3-enyne 3 (1.0 mmol) was added dropwise
to a solution prepared by adding tributylstannane (1.1 mmol) to
Pd(PPh3)4 (0.02 mmol) in THF (2 mL) at room temperature under an
argon atmosphere. After 4 h, the reaction mixture was evaporated
under reduced pressure and the residue was purified by column
chromatography (light petroleum ether/ethyl ether, 4:1) on silica gel.
(5Z,7E)-6-Phenylsulfonyl-7-tributylstannyltetradeca-5,7-diene (4a):
Colourless oil. IR (film): ν (cm–1) 3067, 2957, 2922, 2878, 1587, 1464,
1447, 1304, 1151, 1084, 727, 688; 1H NMR (CDCl3): δ 7.80 (d, J=7.2 Hz,
2H), 7.56–7.44 (m, 3H), 5.63 (t, J=7.2 Hz, 1H), 5.60 (t, J=7.6 Hz,
3JSn–H =56 Hz, 1H), 2.82–2.76 (m, 2H), 1.64–0.84 (m, 47H); 13C NMR
(CDCl3): δ 148.0, 142.1, 140.9, 140.3, 140.2, 132.9, 128.6, 128.1, 31.9, 31.6,
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We thank the National Natural Science Foundation of China
(20862008) for financial support.
Received 12 August 2013; accepted 3 September 2013
Paper 1302122 doi: 10.3184/174751913X13816588007726
Published online: 11 November 2013
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