A stereoselective approach to (Z)-1-Silyl-2-aryl-1,3-dienes from 4-(Phenylselanyl)but-1-yne via palladium-catalyzed silylstannylation and selenoxide elimination

Article abstract of DOI:10.1055/s-0032-1317946

The palladium-catalyzed silylstannylation of 4-(phenylselanyl)but-1-yne proceeded regio- and stereoselectively, followed by selenoxide elimination via oxidation to give (Z)-1-(trimethylsilyl)-2-(tributylstannyl)buta-1,3-diene in good yield. This conjugated diene underwent the Stille coupling reaction with various aryl iodides in the presence of Pd(PPhto afford (Z)-2-aryl-1- (trimethylsilyl)buta-1,3-dienes with high stereoselectivity. Reversing the order of selenoxide elimination and Stille coupling reaction in the synthetic procedure also resulted in good yields of (Z)-2-aryl-1-(trimethylsilyl)buta-1,3- dienes. Georg Thieme Verlag Stuttgart - New York.

Full text of DOI:10.1055/s-0032-1317946

PAPER
▌341
paper
A Stereoselective Approach to (Z)-1-Silyl-2-aryl-1,3-dienes from
4-(Phenylselanyl)but-1-yne via Palladium-Catalyzed Silylstannylation
and Selenoxide Elimination
A Stereoselective Approach to (Z)-1-Silyl-2-aryl-1,3-dienes
Kazuki Shintaku, Hajime Maeda, Masahito Segi*
Division of Material Sciences, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa,
Ishikawa 920-1192, Japan
Fax +81(76)2344800; E-mail: segi@se.kanazawa-u.ac.jp
Received: 08.11.2012; Accepted after revision: 03.12.2012
nylic organocuprates, generated from the transmetalation
of vinylzirconates, containing a phenylselanyl group to
enones, followed by selenoxide elimination via oxida-
tion.13
Abstract: The palladium-catalyzed silylstannylation of 4-(phenyl-
selanyl)but-1-yne proceeded regio- and stereoselectively, followed
by selenoxide elimination via oxidation to give (Z)-1-(trimethylsi-
lyl)-2-(tributylstannyl)buta-1,3-diene in good yield. This conjugat-
ed diene underwent the Stille coupling reaction with various aryl
iodides in the presence of Pd(PPh3)4 to afford (Z)-2-aryl-1-(trimeth-
ylsilyl)buta-1,3-dienes with high stereoselectivity. Reversing the
order of selenoxide elimination and Stille coupling reaction in the
synthetic procedure also resulted in good yields of (Z)-2-aryl-1-(tri-
methylsilyl)buta-1,3-dienes.
Herein, we describe a simple and stereoselective synthesis
of (Z)-1-silyl-2-aryl-1,3-dienes by the combination of pal-
ladium-catalyzed silylstannylation of the terminal triple
bond of 4-(phenylselanyl)but-1-yne (1), oxidative elimi-
nation of the phenylselanyl group, and the Stille coupling
reaction with various aryl iodides (Scheme 1).
Key words: silylstannylation, selenide, Stille coupling reaction,
selenoxide elimination, conjugated dienes, stereoselectivity
Pd(0), Bu3SnSiMe3
SnBu3
THF
Me3Si
SePh
SePh
Conjugated dienes are useful intermediates in organic
synthesis because they can be utilized in numerous trans-
formations,1 such as Diels–Alder reactions, and are fre-
quently found as significant constituents in natural
products and their analogues.2 In particular, functional-
ized 1,3-dienes bearing metals and heteroatoms, for ex-
ample Danishefsky’s diene and Rawal’s diene, can play
an important role in cycloadditions and behave highly ef-
fective tools for the control of regio- and stereoselectivities
by the presence of their functional groups.3 The synthetic
approaches to bimetal-substituted 1,3-dienes, which are
substituted at the 1,2-,4 1,3-,5 2,3-,6 and 1,4-positions,7
containing B, Si, Ge, and Sn, are described in literature.
However, useful methods for the stereoselective synthesis
of silicon/tin 1,2-bimetal-substituted 1,3-dienes are limit-
ed.8
2
1
excess H2O2
THF
Ar
ArI, Pd(PPh3)4
LiCl, CuI, DMF
SnBu3
Me3Si
Me3Si
4
3
Scheme 1
We initiated the investigation by optimizing the reaction
conditions (Pd catalyst, concentration, and reaction time)
for the palladium-catalyzed silylstannylation of 1 (Table
1). The reaction of 1 with trimethyl(tributylstannyl)silane
in the presence of Pd(PPh3)4 (5 mol%) was carried out in
tetrahydrofuran (1.0 M) at 60 °C for 24 hours to give (Z)-
1-silyl-2-stannyl-substituted homoallylic selenide 2 in
34% yield with exclusive regio- and stereoselectivities
(entry 1). Increasing the reaction time did not appreciably
improve the yield of 2 (entries 2 and 3). When the reaction
was conducted using a 2.0 M solution of 1 in tetrahydro-
furan, the desired product 2 was obtained in 43% yield
(entry 4). Changing the catalyst from Pd(PPh3)4 to
Pd(dba)2 and a phosphite or phosphine gave improved
yields (entries 6 and 7), but the use of Pd(PPh3)2Cl2 gave
traces of 2 only (entry 5). The reaction under the best con-
ditions [Pd(dba)2 (2 mol%)/P(OEt3) (4 mol%), THF, 60
°C, 24 hours] afforded the silylstannylated product 2 in
65% yield (entry 6). Unfortunately, the use of the catalyst
combination of Pd2(dba)3·CHCl3 (1 mol%) and triphe-
nylphosphine (4 mol%), which is known to be highly ef-
fective for the silylstannylation of propargylic alcohols
and their derivatives,10g gave an unsatisfactory result in
The palladium-catalyzed silylstannylation of terminal al-
kynes is very interesting and well established,9,10 because
the resulting compounds have two different metal func-
tionalities that can be useful for further transformations,
such as Stille coupling,10g,11 iododestannylation,8,10g,11a,12
Sn–Li exchange reactions,9a,10b,d and Lewis acid mediated
acylation.10d Furthermore, the silylstannylation reaction
generally proceeds with excellent regio- and stereoselec-
tivities to give 1,2-bimetal-substituted alkenes in which
the stannyl group is attached to the inner carbon.10e
Recently, we reported the stereoselective synthesis of
monosubstituted 1,3-dienes via conjugated addition of vi-
SYNTHESIS 2013, 45, 0341–0346
Advanced online publication: 03.01.2013
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X
DOI: 10.1055/s-0032-1317946; Art ID: SS-2012-F0869-OP
© Georg Thieme Verlag Stuttgart · New York

342
K. Shintaku et al.
PAPER
this reaction (entry 8). In all entries, the silylstannylation From the viewpoint of synthetic efficiency, one-pot syn-
of 1 was incomplete and unreacted alkyne 1 was recov- thetic procedures are very useful. A one-pot procedure for
ered. Furthermore, attempts were made to optimize the the palladium-catalyzed silylstannylation of 1 followed
Pd(dba)2/P(OEt)3 catalytic system for this silylstannyl- by the oxidation with hydrogen peroxide was carried out.
ation under various reaction conditions (solvent, reaction However, a vigorously exothermic reaction between the
temperature, and concentration of catalyst) to improve the catalyst [Pd(dba)2/P(OEt)3] and hydrogen peroxide oc-
yield 2. However, the conditions given in entry 6 still gave curred, and the desired product was not obtained.
the best result. The efficiency of the palladium-catalyzed
For further transformations, the Stille coupling reaction at
silylstannylation of 1 was not high, which would be due to
the vinyltin group of the conjugated diene 3 was exam-
the influence of the selenium atom in 1. The configuration
ined. The cross-coupling of 3 with a variety of aryl iodides
(2 equiv) using Pd(PPh3)4 (5 mol%) in the presence of
copper(I) iodide (20 mol%) and lithium chloride (2 equiv)
of 2 was determined to be the trans between tin and the
vinyl proton by the NMR coupling constants [J(117Sn,
H) = 168 Hz and J(119Sn, H) = 176 Hz]. In general, when
as additives in N,N-dimethylformamide at 70 °C gave (Z)-
the proton and tin are in a trans relationship, the coupling
2-aryl-1-(trimethylsilyl)buta-1,3-dienes 4a–f in moderate
constants are 160–200 Hz, whereas the coupling constants
to good yields (Table 2). Stille coupling of 3 with iodo-
benzene, 1-iodonaphthalene, or aryl iodides with an elec-
in cis and geminal geometries are 80–100 Hz.10d,i,14
tron-deficient substituent in the para position provided
Table 1 Palladium-Catalyzed Silylstannylation of 4-(Phenylsela-
the conjugated dienes 4a,b,e,f in 70–84% yields (entries
1, 2, 5, and 6). In the case of 4-methyl- and 4-methoxyphe-
nyl coupling partners, the corresponding products 4c and
4d were obtained, but the yields decreased to 52% and
54%, respectively (entries 3 and 4).
nyl)but-1-yne (1)a
Pd catalyst, Bu3SnSiMe3
THF, 60 °C, time
SnBu3
Me3Si
SePh
SePh
2
1
Table 2 Stille Coupling Reaction of (Z)-1-Silyl-2-stannylbuta-1,3-
diene 3 with Aryl Iodides
Entry
Pd catalyst (mol%)
Pd(PPh3)4 (5)
Time (h) Yieldb (%)
1c
2c
3c
4
24
48
96
24
24
24
24
34
ArI (2 equiv), Pd(PPh3)4 (5 mol%)
LiCl (2 equiv), CuI (20 mol%)
Ar
SnBu3
Pd(PPh3)4 (5)
36
DMF, 70 °C, 4 h
Me3Si
Me3Si
Pd(PPh3)4 (5)
40
3
4
Pd(PPh3)4 (5)
43
Entry
ArI
Product
Yielda (%)
5
Pd(PPh3)2Cl2 (5)
Pd(dba)2 (2)/P(OEt)3 (4)
Pd(dba)2 (2)/Bu3P (4)
trace
65
1
2
3
4
5
6
Ph
4a
4b
4c
4d
4e
4f
70
82
52
54
84
77
6
1-naphthyl
4-MeC6H4
4-MeOC6H4
4-O2NC6H4
4-ClC6H4
7
56
8
Pd2(dba)3·CHCl3 (1)/Ph3P (4) 24
45
a All reactions were carried out with a 2.0 M solution of 1 in THF.
b Isolated yield.
c The reaction was carried out with 1.0 M solution of 1 in THF.
a Isolated yield.
Oxidation of the adduct 2 containing a phenylselanyl
group with hydrogen peroxide in tetrahydrofuran resulted
in syn elimination of the corresponding selenoxide lead-
ing to solely the (Z)-isomer of 1-silyl-2-stannylbuta-1,3-
diene 3 in 96% yield without isomerization of the alkene
moiety (Scheme 2). The stereochemistry of 3 was also as-
signed by the coupling constants between tin and the vinyl
proton [J(117Sn, H) = 162 Hz and J(119Sn, H) = 167 Hz].
On the other hand, reversing the order of the selenoxide
elimination and the Stille coupling reaction in the synthet-
ic sequence also afforded conjugated dienes 4. The cross-
coupling reaction of the silylstannylated product 2 with
various aryl iodides under the same conditions as de-
scribed above gave (Z)-2-aryl-1-(trimethylsilyl)-substitut-
ed homoallylic selenides 5a–f stereoselectively (Table 3).
The Stille coupling reaction with iodobenzene, 1-io-
donaphthalene, and electron-rich aryl iodides resulted the
desired products 5a–d in 63–65% yields (entries 1–4). In
this reaction, the use of electron-deficient aryl iodides was
highly effective (91% and 71% yields, entries 5 and 6, re-
spectively). Next, oxidation of the cross-coupling prod-
ucts 5a–f with hydrogen peroxide afforded efficiently (Z)-
2-aryl-1-(trimethylsilyl)-substituted conjugated dienes
excess H2O2
SnBu3
SnBu3
THF, 25 °C, 2 h
Me3Si
Me3Si
SePh
96%
2
3
Scheme 2
Synthesis 2013, 45, 341–346
© Georg Thieme Verlag Stuttgart · New York

PAPER
A Stereoselective Approach to (Z)-1-Silyl-2-aryl-1,3-dienes
343
MFB-595 apparatus and are uncorrected. Column chromatography
used Kanto Chemical silica gel 60 N (40–50 μm). THF was distilled
from Na benzophenone ketyl under N2. DMF was dried over CaH2
and distilled under reduced pressure. Other reagents were commer-
cially available and used without further purification. All reactions
were performed under an argon atmosphere with flame-dried glass-
ware using a vacuum pump unless otherwise described. 4-(Phenyl-
selanyl)but-1-yne (1)13 and trimethyl(tributylstannyl)silane15 were
synthesized according to published procedures.
4a–f in high yields (78–87%) via syn elimination of the
corresponding selenoxides, regardless of the substituent
on the aromatic ring (Table 4).
Table 3 Stille Coupling Reaction of the Silylstannylated Compound
2 with Aryl Iodides
ArI (2 equiv), Pd(PPh3)4
(5 mol%)
LiCl (2 equiv), CuI
(20 mol%)
DMF, 70 °C, 4 h
Ar
SnBu3
(Z)-Trimethyl[4-(phenylselanyl)-2-(tributylstannyl)but-1-
enyl]silane (2)
Me3Si
Me3Si
SePh
SePh
A THF (5 mL) soln of Pd(dba)2 (0.116 g, 0.202 mmol) and P(OEt)3
(0.069 g, 0.415 mmol) was stirred at r.t. for 5 min. To the mixture
was added trimethyl(tributylstannyl)silane (6.30 g, 17.4 mmol) and
4-(phenylselanyl)but-1-yne (1, 2.19 g, 10.5 mmol). After heating at
60 °C for 24 h, the mixture was cooled to r.t., diluted with Et2O (20
mL), and concentrated. The residue was purified by column chro-
matography (silica gel, hexane) to afford 2 (3.93 g, 65%) as a col-
orless oil.
5
2
Entry
ArI
Product
Yielda (%)
1
2
3
4
5
6
Ph
5a
5b
5c
5d
5e
5f
63
64
65
65
91
71
1-naphthyl
4-MeC6H4
4-MeOC6H4
4-O2NC6H4
4-ClC6H4
IR (neat): 3059, 2853, 1598, 1556, 1477, 1464, 1246, 837, 733, 691
cm–1.
1H NMR (400 MHz, CDCl3): δ = 0.09 (s, 9 H), 0.86–0.92 (m, 15 H),
1.25–1.47 (m, 12 H), 2.62 (t, J = 8.2 Hz, 2 H), 2.86 (t, J = 8.2 Hz, 2
H), 6.41 (s, J(117Sn,H) = 168 Hz, J(119Sn,H) = 176 Hz, 1 H), 7.23–
7.27 (m, 3 H), 7.50–7.52 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 0.1, 11.2, 13.7, 27.4, 27.5, 29.2,
47.2, 126.8, 129.0, 130.4, 133.0, 145.4, 163.5.
a Isolated yield.
77Se NMR (76 MHz, CDCl3): δ = 302.5.
Table 4 Selenoxide Elimination via Oxidation of the Coupling Prod-
ucts 5
LRMS (EI): m/z (%) = 155 (80), 178 (91), 283 (85), 558 (100), 573
(12) [M – 1]+.
HRMS (EI): m/z [M – 3 H]+ calcd for C25H43SiSeSn: 571.1321;
Ar
Ar
excess H2O2, THF, 25 °C, 2 h
Me3Si
found: 571.1319.
Me3Si
SePh
(Z)-Trimethyl[2-(tributylstannyl)buta-1,3-dienyl]silane (3)
To a soln of 2 (0.500 g, 0.874 mmol) in THF (5 mL) was added 30%
aq H2O2 (1.0 mL) at 0 °C. After stirring for 2 h at r.t., the reaction
was quenched with sat. NaHCO3 and extracted with Et2O (2 × 20
mL). The combined organic layers were washed with brine (2 × 20
mL), dried (MgSO4), concentrated, and purified by column chroma-
tography (silica gel, hexane) to afford 3 (0.350 g, 96%) as a color-
less oil.
4
5
Entry
Substrate
Ar
Product
Yielda (%)
1
2
3
4
5
6
5a
5b
5c
5d
5e
5f
Ph
4a
4b
4c
4d
4e
4f
83
78
84
85
86
87
1-naphthyl
4-MeC6H4
4-MeOC6H4
4-O2NC6H4
4-ClC6H4
IR (neat): 3082, 2855, 1607, 1464, 1248, 984, 899, 837 cm–1.
1H NMR (400 MHz, CDCl3): δ = –0.14 (s, 9 H), 0.87–1.01 (m, 15
H), 1.28–1.53 (m, 12 H), 4.93 (dd, J = 1.2, 10.5 Hz, 1 H), 5.04 (dd,
J = 1.2, 17.2 Hz, 1 H), 6.51 (ddd, J = 1.2, 10.5, 17.2 Hz, 1 H), 6.62
(s, J(117Sn,H) = 162 Hz, J(119Sn,H) = 167 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 0.30, 11.7, 13.6, 27.4, 29.1,
113.5, 147.8, 148.8, 162.3.
a Isolated yield.
LRMS (EI): m/z (%) = 73 (67), 177 (79), 235 (85), 291 (100), 359
(47), 416 (21) [M]+.
HRMS (EI): m/z [M]+ calcd for C19H40SiSn: 416.1921; found:
In conclusion, we have developed a simple and useful
method for the stereoselective synthesis of (Z)-1-silyl-2-
aryl-1,3-dienes by the combination of palladium-cata-
lyzed silylstannylation, oxidative deselenation, and the
Stille coupling reaction.
416.1919.
Stille Coupling Reaction; General Procedure
A 3-necked flask was charged with LiCl (0.024 g, 0.566 mmol) and
flame-dried under vacuum. After cooling, Pd(PPh3)4 (0.015 g, 0.013
mmol) and CuI (0.011 g, 0.578 mmol) were added, then the mixture
was degassed with an argon purge. A soln of an aryl iodide (0.5
mmol) and the alkenylstannnane 3 or 2 (0.25 mmol) in DMF (5mL)
was introduced, and the mixture was heated at 70 °C for 4 h. After
cooling to r.t., the mixture was diluted with E2O (30 mL) and
washed with H2O (20 mL). The aqueous layer was further extracted
with Et2O (2 × 20 mL). The combined organic layers were washed
with H2O (2 × 20 mL) and brine (2 × 20 mL), dried (MgSO4), and
concentrated. The residue was purified by column chromatography
1H, 13C, and 77Se NMR spectra were recorded on a Jeol JNM-LA-
400 (1H; 399.7 MHz, 13C; 100.4 MHz, and 77Se; 76.2 MHz, respec-
tively) spectrometer relative to TMS or the residual solvent signals
[CDCl3: δ = 7.26 (1H) and 77.0 (13C)] as internal standard, or
(PhSe)2 as external standard [CDCl3: δ = 464.1 (77Se)]. IR spectra
were obtained on a Shimadzu FTIR-8300 spectrophotometer. Mass
spectra (EI) were recorded on a Jeol JMS-700 or JMS-SX 102A
mass spectrometer. Melting points were measured on a Gallenkamp
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 341–346

344
K. Shintaku et al.
PAPER
(silica gel, hexane–EtOAc, 1:0–20:1) to afford the cross-coupling
product.
IR (KBr): 3078, 2955, 1597, 1570, 1512, 1342, 1246, 868, 833
cm–1.
1H NMR (400 MHz, CDCl3): δ = –0.18 (s, 9 H), 4.61 (d, J = 17.4
Hz, 1 H), 5.15 (d, J = 10.5 Hz, 1 H), 5.95 (s, 1 H), 6.60 (dd, J = 10.5,
17.4 Hz, 1 H), 7.32 (d, J = 8.1 Hz, 2 H), 8.22 (d, J = 8.1 Hz, 2 H).
13C NMR (100 MHz, CDCl3): δ = –0.28, 117.4, 123.1, 130.4, 135.9,
142.2, 147.1, 147.5, 153.8.
(Z)-Trimethyl(2-phenylbuta-1,3-dienyl)silane (4a)
Colorless oil; yield: 35 mg (70%).
IR (neat): 3089, 2955, 2897, 1562, 1493, 1246, 860, 837 cm–1.
1H NMR (400 MHz, CDCl3): δ = –0.19 (s, 9 H), 4.74 (d, J = 17.3
Hz, 1 H), 5.11 (d, J = 10.5 Hz, 1 H), 5.85 (s, 1 H), 6.61 (dd, J = 10.5,
17.3 Hz, 1 H), 7.12–7.14 (m, 2 H), 7.29–7.33 (m, 3 H).
13C NMR (100 MHz, CDCl3): δ = –0.29, 117.0, 127.1, 127.7, 129.4,
134.2, 140.1, 143.0, 156.3.
LRMS (EI): m/z (%) = 43 (82), 118 (73), 180 (70), 232 (100), 247
(90) [M]+.
HRMS (EI): m/z [M]+ calcd for C13H17O2NSi: 247.1029; found:
247.1031.
LRMS (EI): m/z (%) = 43 (94), 118 (84), 135 (91), 187 (100), 202
(95) [M]+.
(Z)-[2-(4-Chlorophenyl)buta-1,3-dienyl]trimethylsilane (4f)
Pale yellow oil; yield: 45 mg (77%).
IR (neat): 3090, 2955, 2897, 1597, 1489, 1246, 860, 833 cm–1.
HRMS (EI): m/z [M]+ calcd for C13H18Si: 202.1178; found:
202.1180.
1H NMR (400 MHz, CDCl3): δ = –0.18 (s, 9 H), 4.69 (d, J = 17.2
Hz, 1 H), 5.11 (d, J = 10.4 Hz, 1 H), 5.86 (s, 1 H), 6.58 (dd, J = 10.4,
17.2 Hz, 1 H), 7.07 (dd, J = 2.0, 6.3 Hz, 2 H), 7.32 (dd, J = 2.0, 6.3
Hz, 2 H).
13C NMR (100 MHz, CDCl3): δ = –0.21, 117.0, 128.0, 130.8, 133.0,
135.0, 138.6, 142.8, 155.0.
(Z)-Trimethyl[2-(1-naphthyl)buta-1,3-dienyl]silane (4b)
Colorless oil; yield: 52 mg (82%).
IR (neat): 3044, 2955, 2897, 1562, 1246, 864, 837, 779 cm–1.
1H NMR (400 MHz, CDCl3): δ = –0.37 (s, 9 H), 4.54 (d, J = 17.4
Hz, 1 H), 5.06 (d, J = 10.4 Hz, 1 H), 6.14 (s, 1 H), 6.74 (dd, J = 10.4,
17.4 Hz, 1 H), 7.23 (d, J = 6.0 Hz, 1 H), 7.41–7.48 (m, 3 H), 7.78–
7.84 (m, 3 H).
13C NMR (100 MHz, CDCl3): δ = –0.75, 117.1, 125.1, 125.6, 125.6,
126.5, 127.0, 127.5, 128.0, 135.9, 142.9.
LRMS (EI): m/z (%) = 59 (65), 73 (45), 169 (99), 221 (100), 236
(95) [M]+.
HRMS (EI): m/z [M]+ calcd for C13H17SiCl: 236.0788; found:
236.0792.
LRMS (EI): m/z (%) = 73 (91), 152 (40), 165 (65), 178 (99), 185
(67), 209 (26), 221 (45), 237 (55), 252 (100) [M]+.
(Z)-Trimethyl[2-phenyl-4-(phenylselanyl)but-1-enyl]silane (5a)
Colorless oil; yield: 57 mg (63%).
HRMS (EI): m/z [M]+ calcd for C17H20Si: 252.1334; found:
252.1336.
IR (neat): 3055, 2951, 2897, 1593, 1477, 1439, 1246, 841, 737, 702
cm–1.
1H NMR (400 MHz, CDCl3): δ = –0.20 (s, 9 H), 2.78 (t, J = 8.0 Hz,
2 H), 2.89 (t, J = 8.0 Hz, 2 H), 5.59 (s, 1 H), 7.10–7.13 (m, 2 H),
7.20–7.28 (m, 6 H), 7.40–7.42 (m, 2 H).
(Z)-Trimethyl[2-(p-tolyl)buta-1,3-dienyl]silane (4c)
Colorless oil; yield: 28 mg (52%).
IR (neat): 3028, 2955, 2924, 1608, 1246, 864, 841 cm–1.
1H NMR (400 MHz, CDCl3): δ = –0.18 (s, 9 H), 2.37 (s, 3 H), 4.76
(d, J = 17.6 Hz, 1 H), 5.10 (d, J = 10.4 Hz, 1 H), 5.82 (s, 1 H), 6.60
(dd, J = 10.4, 17.6 Hz, 1 H), 7.01 (d, J = 8.0 Hz, 2 H), 7.13 (d,
J = 8.0 Hz, 2 H).
13C NMR (100 MHz, CDCl3): δ = –0.04, 25.6, 43.1, 126.7, 127.2,
127.9, 128.1, 128.8, 129.0, 130.3, 132.5, 142.9, 157.5.
77Se NMR (76 MHz, CDCl3): δ = 298.0.
13C NMR (100 MHz, CDCl3): δ = –0.20, 21.2, 116.8, 128.4, 129.3,
134.1, 136.6, 137.1, 143.1, 156.4.
LRMS (EI): m/z (%) = 73 (100), 105 (8), 135 (13), 187 (12), 215
(5), 287 (26), 360 (19) [M]+.
HRMS (EI): m/z [M]+ calcd for C19H24SiSe: 360.0812; found:
360.0817.
LRMS (EI): m/z (%) = 73 (63), 91 (66), 119 (100), 149 (80), 201
(71), 216 (70) [M]+.
HRMS (EI): m/z [M]+ calcd for C14H20Si: 216.1334; found:
216.1336.
(Z)-Trimethyl[2-(1-naphthyl)-4-(phenylselanyl)but-1-enyl]si-
lane (5b)
Pale yellow oil; yield: 66 mg (64%).
(Z)-[2-(4-Methoxyphenyl)buta-1,3-dienyl]trimethylsilane (4d)
Colorless oil; yield: 31 mg (54%).
IR (neat): 3055, 2951, 1609, 1578, 1477, 1246, 837, 779, 733, 691
cm–1.
1H NMR (400 MHz, CDCl3): δ = –0.37 (s, 9 H), 2.87–2.91 (m, 2 H),
2.95–2.99 (m, 2 H), 5.92 (s, 1 H), 7.19–7.22 (m, 4 H), 7.39–7.47 (m,
5 H), 7.78 (d, J = 8.3 Hz, 1 H), 7.83–7.86 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = –0.57, 25.7, 43.1, 125.0, 125.7,
125.8, 125.9, 126.6, 127.4, 128.2, 129.0, 130.4, 130.7, 131.5, 132.3,
133.5, 140.4, 155.7.
IR (neat): 3090, 2955, 2897, 1612, 1508, 1288, 1246, 1173, 1038,
864, 837 cm–1.
1H NMR (400 MHz, CDCl3): δ = –0.17 (s, 9 H), 3.83 (s, 3 H), 4.77
(d, J = 17.3 Hz, 1 H), 5.10 (d, J = 10.7 Hz, 1 H), 5.82 (s, 1 H), 6.60
(dd, J = 10.7, 17.3 Hz, 1 H), 6.87 (d, J = 8.8 Hz, 2 H), 7.05 (d,
J = 8.8 Hz, 2 H).
13C NMR (100 MHz, CDCl3): δ = –0.18, 55.2, 113.1, 116.7, 130.5,
132.5, 134.2, 143.2, 156.0, 158.7.
77Se NMR (76 MHz, CDCl3): δ = 298.0.
LRMS (EI): m/z (%) = 73 (100), 180 (57), 252 (9), 337 (2), 410 (7)
LRMS (EI): m/z (%) = 43 (72), 118 (76), 165 (99), 217 (96), 232
[M]+.
(100) [M]+.
HRMS (EI): m/z [M]+ calcd for C23H26SiSe: 410.0969; found:
410.0968.
HRMS (EI): m/z [M]+ calcd for C14H20OSi: 232.1284; found:
232.1278.
(Z)-Trimethyl[4-(phenylselanyl)-2-(p-tolyl)but-1-enyl]silane
(Z)-Trimethyl[2-(4-nitrophenyl)buta-1,3-dienyl]silane (4e)
Pale yellow solid; yield: 52 mg (84%); mp 69–70 °C.
(5c)
Colorless oil; yield: 61 mg (65%).
Synthesis 2013, 45, 341–346
© Georg Thieme Verlag Stuttgart · New York

PAPER
A Stereoselective Approach to (Z)-1-Silyl-2-aryl-1,3-dienes
345
IR (neat): 3055, 2951, 2897, 1597, 1578, 1477, 1246, 841, 733, 691
cm–1.
1H NMR (400 MHz, CDCl3): δ = –0.17 (s, 9 H), 2.35 (s, 3 H), 2.78
(t, J = 8.0 Hz, 2 H), 2.90 (t, J = 8.0 Hz, 2 H), 5.57 (s, 1 H), 7.02 (d,
J = 8.1 Hz, 2 H), 7.10 (d, J = 8.1 Hz, 2 H), 7.22–7.26 (m, 3 H),
7.42–7.44 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 0.04, 21.2, 25.7, 43.1, 126.6,
128.0, 128.4, 128.5, 128.9, 130.4, 132.4, 136.8, 139.9, 157.6.
77Se NMR (76 MHz, CDCl3): δ = 298.1.
Selenoxide Elimination (4 from 5); General Procedure
To a soln of 5 (0.15 mmol) in THF (5 mL) was added 30% aq H2O2
(0.3 mL) at 0 °C. After stirring for 2 h at r.t., the reaction was
quenched with sat. NaHCO3 and extracted with Et2O (2 × 20 mL).
The combined organic layers were washed with brine (2 × 20 mL),
dried (MgSO4), concentrated, and purified by column chromatogra-
phy (silica gel, hexane) to afford 4. Yields: 4a: 25 mg (83%); 4b: 30
mg (78%); 4c: 27 mg (84%); 4d: 30 mg (85%); 4e: 32 mg (86%);
4f: 31 mg (87%).
LRMS (EI): m/z (%) = 73 (100), 115 (11), 149 (12), 301 (22), 374
(19) [M]+.
Acknowledgment
HRMS (EI): m/z [M]+ calcd for C20H26SiSe: 374.0969; found:
374.0965.
This work was partially supported by Grant-in-Aids for Scientific
Research (C) from the Ministry of Education, Culture, Sports, Sci-
ence and Technology (MEXT) of Japan and by the Collaborative
Research Program of Institute for Chemical Research, Kyoto Uni-
versity (grant # 2012-9).
(Z)-[2-(4-Methoxyphenyl)-4-(phenylselanyl)but-1-enyl]tri-
methylsilane (5d)
Pale yellow oil; yield: 63 mg (65%).
IR (neat): 3055, 2951, 2835, 1609, 1508, 1246, 1173, 837, 737, 691
cm–1.
1H NMR (400 MHz, CDCl3): δ = –0.17 (s, 9 H), 2.77 (t, J = 8.0 Hz,
2 H), 2.89 (t, J = 8.0 Hz, 2 H), 3.81 (s, 3 H), 5.56 (s, 1 H), 6.82 (d,
J = 8.4 Hz, 2 H), 7.05 (d, J = 8.4 Hz, 2 H), 7.22–7.25 (m, 3 H),
7.41–7.44 (m, 2 H).
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synthesis.SnoIufproi
m
tgioSrantnugIifoop
r
itmnatr
References
13C NMR (100 MHz, CDCl3): δ = 0.07, 25.8, 43.1, 55.2, 113.2,
126.6, 128.5, 129.0, 129.2, 130.4, 132.5, 135.2, 157.2, 158.8.
77Se NMR (76 MHz, CDCl3): δ = 297.8.
(1) (a) Fringuelli, F.; Taticchi, A. Dienes in the Diels–Alder
Reaction; Wiley: New York, 1990. (b) Oppolzer, W.
Comprehensive Organic Synthesis; Vol. 5; Trost, B. M.;
Fleming, I., Eds.; Pergamon Press: Oxford, 1991, 315.
(c) Larock, R. C. Comprehensive Organic Transformations,
2nd ed.; Wiley: New York, 1999, 463. (d) Fringuelli, F.;
Taticchi, A. The Diels–Alder Reaction: Selected Practical
Methods; John Wiley & Sons: Chichester, 2002. (e) Welker,
M. E. Tetrahedron 2008, 64, 11529.
(2) (a) Negishi, E.; Owczarczyk, Z. Tetrahedron Lett. 1991, 32,
6683. (b) Murakami, N.; Wang, W.; Aoki, M.; Tsutsui, Y.;
Sugimoto, M.; Kobayashi, M. Tetrahedron Lett. 1998, 39,
2349. (c) Zeng, F.; Negishi, E. Org. Lett. 2001, 3, 719.
(d) Hu, T.; Panek, J. S. J. Am. Chem. Soc. 2002, 124, 11368.
(e) Murray, T. J.; Forsyth, C. J. Org. Lett. 2008, 10, 3429.
(f) Matovic, M. J.; Hayes, P. Y.; Penman, K.; Lehmann, R.
P.; De Voss, J. J. J. Org. Chem. 2011, 76, 4467.
(3) (a) Danishefsky, S. Acc. Chem. Res. 1981, 14, 400.
(b) Taddei, M.; Mann, A. Tetrahedron Lett. 1986, 27, 2913.
(c) Nativi, C.; Taddei, M. Tetrahedron 1989, 45, 1131.
(d) Aversa, M. C.; Barattucci, A.; Bonaccorsi, P.; Giannetto,
P. J. Org. Chem. 1997, 62, 4376. (e) Kozmin, S. A.; Janey,
J. M.; Rawal, V. H. J. Org. Chem. 1999, 64, 3039.
(4) (a) Suginome, M.; Matsuda, T.; Nakamura, H.; Ito, Y.
Tetrahedron 1999, 55, 8787. (b) Lüken, C.; Moberg, C. Org.
Lett. 2008, 10, 2505. (c) Botvinik, A.; Quntar, A. A.;
Rubinstein, A.; Srebnik, M. J. Organomet. Chem. 2009, 694,
3349. (d) Singidi, R. R.; RajanBabu, T. V. Org. Lett. 2010,
12, 2622.
LRMS (EI): m/z (%) = 73 (100), 115 (9), 165 (11), 217 (16), 317
(18), 390 (19) [M]+.
HRMS (EI): m/z [M]+ calcd for C20H26OSiSe: 390.0918; found:
390.0919.
(Z)-Trimethyl[2-(4-nitrophenyl)-4-(phenylselanyl)but-1-
enyl]silane (5e)
Yellow oil; yield: 92 mg (91%).
IR (neat): 3091, 2954, 1595, 1516, 1310, 1010, 853, 837, 735 cm–1.
1H NMR (400 MHz, CDCl3): δ = –0.17 (s, 9 H), 2.80–2.82 (m, 2 H),
2.85–2.88 (m, 2 H), 5.74 (s, 1 H), 7.24–7.26 (m, 3 H), 7.31 (d,
J = 8.5 Hz, 2 H), 7.43–7.46 (m, 2 H), 8.18 (d, J = 8.5 Hz, 2 H).
13C NMR (100 MHz, CDCl3): δ = –0.05, 25.3, 42.6, 123.3, 124.8,
127.0, 129.0, 129.1, 131.5, 132.8, 138.7, 150.0, 154.9.
77Se NMR (76 MHz, CDCl3): δ = 299.4.
LRMS (EI): m/z (%) = 73 (66), 171 (40), 332 (97), 390 (56), 405
(100) [M]+.
HRMS (EI): m/z [M]+ calcd for C19H23O2NSiSe: 405.0663; found:
405.0661.
(Z)-[2-(4-Chlorophenyl)-4-(phenylselanyl)but-1-enyl]trimeth-
ylsilane (5f)
Pale yellow oil; yield: 70 mg (71%).
IR (neat): 3059, 2953, 1609, 1580, 1477, 1248, 1090, 839, 735, 691
cm–1.
1H NMR (400 MHz, CDCl3): δ = –0.17 (s, 9 H), 2.75–2.78 (m, 2 H),
2.86–2.89 (m, 2 H), 5.63 (s, 1 H), 7.06 (d, J = 8.3 Hz, 2 H), 7.23–
7.28 (m, 5 H), 7.41–7.43 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 0.01, 25.5, 42.9, 126.8, 128.1,
129.0, 129.4, 129.8, 130.1, 132.6, 133.0, 141.3, 156.1.
(5) (a) Wang, K. K.; Chu, K.-H.; Lin, Y.; Chen, J.-H.
Tetrahedron 1989, 45, 1105. (b) Mazal, C.; Vaultier, M.
Tetrahedron Lett. 1994, 35, 3089.
(6) (a) Reich, H. J.; Reich, I. L.; Yelm, K. E.; Holladay, J. E.;
Gschneidner, D. J. Am. Chem. Soc. 1993, 115, 6625. (b) Cai,
M.-Z.; Zhoh, Z.; Wang, P.-P. Synthesis 2006, 789.
(7) (a) Murakami, M.; Yoshida, T.; Kawanami, S.; Ito, Y. J. Am.
Chem. Soc. 1995, 117, 6408. (b) Onozawa, S.; Hatanaka, Y.;
Choi, N.; Tanaka, M. Organometallics 1997, 16, 5389.
(c) Suginome, M.; Matsuda, T.; Ito, Y. Organometallics
1998, 17, 5233. (d) Coleman, R. S.; Walczak, M. C. Org.
Lett. 2005, 7, 2289.
77Se NMR (76 MHz, CDCl3): δ = 298.1.
MS (EI): m/z (%) = 73 (100), 129 (7), 169 (14), 221 (9), 321 (29),
394 (19) [M]+.
HRMS (EI): m/z [M]+ calcd for C19H23SiSeCl: 394.0423; found:
394.0422.
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 341–346

346
K. Shintaku et al.
PAPER
(8) Mandal, A. K.; Schneekloth, J. S. Jr; Kuramochi, K.; Crews,
C. M. Org. Lett. 2006, 8, 427.
Matsuda, T.; Itami, K.; Ashida, S.; Terayama, M. Synthesis
2004, 1522. (i) Endo, T.; Sasaki, F.; Hara, H.; Suzuki, J.;
Tamura, S.; Nagata, Y.; Iyoshi, T.; Saigusa, A.; Nakano, T.
Appl. Organomet. Chem. 2007, 21, 183.
(9) For synthesis of natural products via palladium-catalyzed
silylstannylation, see ref. 7 and: (a) Overman, L. E.; Wild, H.
Tetrahedron Lett. 1989, 30, 647. (b) Cid, M. B.; Pattenden,
G. Tetrahedron Lett. 2000, 41, 7373. (c) Graf, K. M.; Tabor,
M. G.; Brown, M. L.; Paige, M. Org. Lett. 2009, 11, 5382.
(10) (a) Mitchell, T. N.; Killing, H.; Dicke, R.; Wickenkamp, R.
J. Chem. Soc., Chem. Commun. 1985, 354. (b) Mitchell, T.
N.; Wickenkamp, R.; Amamria, A.; Dicke, R.; Schneider, U.
J. Org. Chem. 1987, 52, 4868. (c) Chenard, B. L.; Laganis,
E. D.; Davidson, F.; RajanBabu, T. V. J. Org. Chem. 1985,
50, 3666. (d) Chenard, B. L.; Van Zyl, C. M. J. Org. Chem.
1986, 51, 3561. (e) Hada, M.; Tanaka, Y.; Ito, M.;
(11) (a) Lunot, S.; Thibonnet, J.; Duchêne, A.; Parrain, J.-L.;
Abarbri, M. Tetrahedron Lett. 2000, 41, 8893. (b) Timbart,
L.; Cintrat, J.-C. Chem. Eur. J. 2002, 8, 1637. (c) Thibonnet,
J.; Abarbri, M.; Parrain, J.-L.; Duchêne, A. Tetrahedron
2003, 59, 4433.
(12) Apte, S.; Radetich, B.; Shin, S.; RajanBabu, T. V. Org. Lett.
2004, 6, 4053.
(13) Segi, M.; Suzuki, M.; Shintaku, K.; Maeda, H. Heteroat.
Chem. 2011, 22, 545.
(14) Mitchell, T. N.; Amamria, A.; Killing, H.; Rutschow, D.
J. Organomet. Chem. 1986, 304, 257.
(15) Warren, S.; Chow, A.; Fraenkel, G.; RajanBabu, T. V. J. Am.
Chem. Soc. 2003, 125, 15402.
Murakami, M.; Amii, H.; Ito, Y.; Nakatsuji, H. J. Am. Chem.
Soc. 1994, 116, 8754. (f) Hemeon, I.; Singer, R. D. J. Mol.
Catal. A: Chem. 2004, 214, 33. (g) Nielsen, T. E.; Quement,
S. L.; Tanner, D. Synthesis 2004, 1381. (h) Murakami, M.;
Synthesis 2013, 45, 341–346
© Georg Thieme Verlag Stuttgart · New York