Stereoselective synthesis of difunctionalized 1,3-dienes containing silicon and selenium via hydrozirconation of (Z)-3-(Trimethylsilyl)alk-3-en-1-ynes

Article abstract of DOI:10.1080/00397910802654864

Sonogashira coupling of (E) - iodovinylsilanes 1 with (trimethylsilyl)- acetylene gave (Z)-1,3-bis(trimethylsilyl)alk-3-en-1-ynes 2, which underwent a desilylation reaction to afford (Z)-3-(trimethylsilyl)alk-3-en-1-ynes 3 in good yields. (1E,3Z)-1-Arylse

Full text of DOI:10.1080/00397910802654864

Synthetic Communications1, 39: 2378–2391, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910802654864
Stereoselective Synthesis of Difunctionalized
1,3-Dienes Containing Silicon and Selenium via
Hydrozirconation of (Z)-3-(Trimethylsilyl)alk-
3-en-1-ynes
Xinglin Ye,1,2 Pingping Wang,2 Jiaqin Liu,1 and Mingzhong Cai1
1Department of Chemistry, Jiangxi Normal University,
Nanchang, China
2Department of Chemistry, Jiujiang University, Jiujiang, China
Abstract: Sonogashira coupling of (E)-a-iodovinylsilanes 1 with (trimethylsilyl)-
acetylene gave (Z)-1,3-bis(trimethylsilyl)alk-3-en-1-ynes 2, which underwent a desi-
lylation reaction to afford (Z)-3-(trimethylsilyl)alk-3-en-1-ynes 3 in good yields.
(1E,3Z)-1-Arylseleno-3-(trimethylsilyl)-substituted 1,3-dienes 5 could be synthe-
sized stereoselectively via hydrozirconation of (Z)-3-(trimethylsilyl)alk-3-en-1-ynes
3, followed by trapping with arylselenenyl bromides.
Keywords: Difunctionalized 1,3-diene, hydrozirconation, (E)-a-iodovinylsilane,
Sonogashira coupling, stereoselective synthesis
INTRODUCTION
The stereocontrolled synthesis of 1,3-dienes containing metal or hetero-
atom functional groups is of considerable interest 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-dienyl sulfides,[1] 1,3-dienyl selenides,[2]
1,3-dienylsilanes,[3] and 1,3-dienylstannanes[4] has already been described
in the literature. Recently, the synthesis of difunctionalized 1,3-dienes has
Received September 30, 2008.
Address correspondence to Mingzhong Cai, Department of Chemistry, Jiangxi
Normal University, Nanchang 330022, China. E-mail: caimzhong@163.com
2378

Difunctionalized 1,3-Dienes
2379
also attracted great interest in organic synthesis because such dienes may
find use as synthetic building blocks.[5] In addition, difunctionalized
1,3-dienes containing heteroatoms can control both regio- and stereoselec-
tivity and play a very important role in cycloadditions.[6] Su and coworkers
reported the stereoselective synthesis of 2-alkoxy-3-alkyl(aryl)thiobuta-
1,3-dienes by Negishi coupling between a-alkyl(aryl)thio vinyl zinc
chloride and a-bromo vinyl ether.[7] Coleman and Walczak reported the
stereoselective synthesis of (E,E)-1-tributylstannyl-4-boryl-buta-1,3-diene
and its use as an orthogonal Stille and Suzuki–Miyaura coupling partner.[8]
Very recently, we described the stereoselective synthesis of (Z,Z)-2-silyl-3-
stannyl-substituted 1,3-dienes via the hydromagnesiation of alkynylsilanes,
followed by the cross-coupling reaction with (E)-a-iodovinylstannanes in
the presence of Pd(PPh3)4 catalyst.[9] However, to the best of our knowl-
edge, no well-established method was used to prepare stereoselectively
the silicon=selenium 1,3-bis-metallo-1,3-dienes. Herein, we report that
(1E,3Z)-1-arylseleno-3-(trimethylsilyl)-substituted 1,3-dienes could be
conveniently synthesized via hydrozirconation of (Z)-3-(trimethylsilyl)alk-
3-en-1-ynes, followed by trapping with arylselenenyl bromides.
RESULTS AND DISCUSSION
There has been a lively interest in terminal conjugated enynes, alk-3-en-1-
ynes, because of their synthetic utility; the acetylenic hydrogen can be
converted into various functionalities as well as undergo carbon–carbon
bond formation. Furthermore, the terminal conjugated enyne is a useful
building block for the synthesis of natural products in organic synthesis,
because the terminal conjugated enyne unit occurs in natural products
such as laurencin,[10] dactylyne,[11] quinolizidine,[12] and histrionico-
toxin.[13] Very recently, Hoshi et al. reported the synthesis of terminal
conjugated enynes via Cu-mediated Suzuki–Miyaura cross-coupling reac-
tion of alkenyldialkylboranes with (trimethylsilyl)ethynyl bromide.[14]
Our methodology involves the preparation and the reactions of the
building block (Z)-3-(trimethylsilyl)alk-3-en-1-ynes 3, which can be
conveniently obtained according to Scheme 1.
Scheme 1. Synthesis of (Z)-3-(trimethylsilyl)alk-3-en-l-ynes.

2380
X. Ye et al.
Sonogashira coupling of alkenyl halides with terminal alkynes
provides a simple and general route for the synthesis of conjugated
enynes.[15] We observed that when the coupling reactions of (E)-a-iodovi-
nylsilanes 1 with (trimethylsilyl)acetylene were performed in piperidine at
room temperature using Pd(PPh3)4 and CuI as cocatalyst, fairly rapid
reactions occurred, affording stereoselectively the desired (Z)-1,3-bis
(trimethylsilyl)alk-3-en-1-ynes 2 in good yields. The typical results are
summarized in Table 1. Kusumoto et al.[16] reported that the desilylation
reaction of (E)-1,2,4-tri(trimethylsilyl)but-1-en-3-yne with KF in metha-
nol afforded (E)-1,2-bis(trimethyl-silyl)but-1-en-3-yne; the desilylation
reaction occurred selectively at acetylenic carbon atom. We investigated
the desilylation reaction of (Z)-1,3-bis(trimethylsilyl)-alk-3-en-1-ynes 2
with KF in methanol to prepare (Z)-3-(trimethylsilyl)alk-3-en-1-ynes 3.
We found that the desilylation reaction of (Z)-1,3-bis(trimethylsilyl)-
alk-3-en-1-ynes 2 with KF proceeded smoothly in methanol at 70ꢀC to
give the desired (Z)-3-(trimethylsilyl)alk-3-en-1-ynes 3 in good yields.
The typical results are also summarized in Table 1.
Hydrozirconation has emerged as a unique hydrometallation with
some attractive features such as the good regioselectivity and stereoselec-
tivity observed with alkynes[17] and heteroatom-substituted alkynes.[18]
However, the hydrozirconation of terminal conjugated enynes has
received less attention.[19] With
a convenient route to (Z)-3-
(trimethylsilyl)alk-3-en-1-ynes 3, we decided to establish the feasibility
Table 1. Coupling reaction of 1 with (trimethylsilyl)acetylenea
and desilylation of 2b
Entry
R
Product
Yield (%)c
1
2
3
4
5
6
7
8
n-Bu
Ph
CH3OCH2
n-C6H13
n-Bu
Ph
CH3OCH2
n-C6H13
2a
2b
2c
2d
3a
3b
3c
3d
92
90
88
91
88
87
85
89
aThe reaction of 1 (2 mmol) with (trimethylsilyl)acetylene
(3 mmol) was carried out using Pd(PPh3)4 (0.1 mmol), CuI
(0.2 mmol), and piperidine (6 mL) at room temperature for 2 h.
bThe desilylation reaction of 2 (1 mmol) with KF (10 mmol)
was performed in methanol (4 mL) at 70ꢀC for 5 h.
cIsolated yield of 2 based on the 1 used.

Difunctionalized 1,3-Dienes
2381
Scheme 2. Synthesis of (1E,3Z)-1-arylseleno-3-(trimethylsilyl)-substituted 1,3-
dienes.
of using 3 in a hydrozirconation reaction with Cp2Zr(H)Cl. We observed
that when the hydrozirconation of 3 with Cp2Zr(H)Cl was performed in
tetrahydrofuran (THF) at room temperature, fairly rapid reactions
occurred,
affording
stereoselectively
(1E,3Z)-3-(trimethylsilyl)-
substituted 1,3-dienylzirconium(IV) complexes 4. The intermediates 4
were then trapped with arylselenenyl bromides to give stereoselectively
(1E,3Z)-1-arylseleno-3-(trimethylsilyl)-substituted 1,3-dienes 5 in good
yields (Scheme 2). The typical results are summarized in Table 2. As
shown in Table 2, a variety of (1E,3Z)-1-arylseleno-3-(trimethylsilyl)-
substituted 1,3-dienes 5 could be synthesized stereoselectively via
hydrozirconation of (Z)-3-(trimethylsilyl)alk-3-en-1-ynes 3, followed by
trapping with arylselenenyl bromides. The (1E)-configuration of com-
1
pounds 5 has been proved by their H NMR spectra, which show two
doublets at d ¼ 6.53–7.02 with a coupling constant of 15.6–16.0 Hz, and
this also indicates that hydrozirconation of (Z)-3-(trimethylsilyl)alk-3-
en-1-ynes 3 with Cp2Zr(H)Cl occurs highly regio- and stereoselectively,
affording intermediates 4. In addition, the (3Z)-configuration of com-
pound 5a was confirmed by nuclear Overhauser effect spectroscopy
(NOESY) experiments. An enhancement of the allylic protons was
Table 2. Synthesis of (1E,3Z)-1-arylseleno-3-(trimethylsilyl)-substituted
1,3-dienes 5a–j
Entry
R
Ar
Product
Yielda (%)
1
2
3
4
5
6
7
8
9
10
n-C4H9
n-C4H9
n-C4H9
Ph
Ph
Ph
n-C6H13
n-C6H13
n-C6H13
CH3OCH2
Ph
5a
5b
5c
5d
5e
5f
80
76
81
80
83
75
74
81
84
67
4-ClC6H4
4-CH3C6H4
Ph
4-ClC6H4
4-CH3C6H4
Ph
4-ClC6H4
4-CH3C6H4
Ph
5g
5h
5i
5j
aIsolated yield based on the 3 used.

2382
X. Ye et al.
Scheme 3. Synthesis of (1E,3Z)-phenyl-3-(trimethylsilyl)-1,3-octadiene.
observed as the vinylic proton (d ¼ 5.82 ppm) of 5a was irradiated. There
was a correlation between the allylic protons and the methyl protons of
the trimethylsilyl. A correlation between the vinylic proton (d ¼ 5.82 ppm)
and one other vinylic proton (d ¼ 6.58 ppm) was also observed. The NOE
results indicate that 5a has the expected (1E,3Z)-configuration.
We have also carried out the Ni-catalyzed cross-coupling reaction of
compound 5a with phenylmagnesium bromide in diethyl ether to afford
the selenium-free (1Z,3E)-2-(trimethylsilyl)-substituted 1,3-diene 6 in
84% yield (Scheme 3).
EXPERIMENTAL
General
1H NMR spectra were recorded on a Bruker AC-P400 (400-MHz)
spectrometer with tetramethylsilane (TMS) as an internal standard using
CDCl3 as the solvent. 13C NMR (100-MHz) spectra were recorded on a
Bruker AC-P400 (400-MHz) spectrometer using CDCl3 as the solvent.
Infrared (IR) spectra were determined on an FTS-185 instrument as
neat films. Mass spectra (MS) were obtained on a Finnigan 8239 mass
spectrometer. Microanalyses were measured using a Yanaco MT-3
CHN microelemental analyzer. All reactions were carried out in predried
glassware (150ꢀC, 4 h) and cooled under a stream of dry Ar. All solvents
were dried, deoxygenated, and freshly distilled before use. (E)-a-Iodovi-
nylsilanes 1 were prepared from alkynylsilanes according to the literature
procedure.[20]
General Procedure for the Synthesis of (Z)-1,3-Bis(trimethylsilyl)alk-
3-en-1-ynes 2a–d
(E)-a-Iodovinylsilane 1 (2.0 mmol), Pd(PPh3)4 (0.1 mmol), piperidine
(6 mL), and CuI (0.2 mmol) were added to a flask under Ar, and the

Difunctionalized 1,3-Dienes
2383
resulting mixture was stirred at room temperature for 5 min. (Trimethyl-
silyl)acetylene (3.0 mmol) was added to this solution, and the reaction
mixture was stirred at room temperature for 2 h, quenched with sat.
NH4Cl aq. solution (10 mL) at 0ꢀC, and extracted with Et2O (2 ꢁ 25 mL).
The ethereal solution was washed with water (2 ꢁ 10 mL) and dried over
MgSO4. The solvent was removed under vacuum, and the residue was
purified by flash chromatography on silica gel, eluting with light
petroleum ether (bp 30–60ꢀC).
Data
(Z)-1,3-Bis(trimethylsilyl)oct-3-en-1-yne (2a)
Oil. IR (film): n (cmꢂ1) 2959, 2928, 2120, 1719, 1581, 1406, 1249, 841,
1
759; H NMR (CDCl3): d 6.71 (t, J ¼ 7.6 Hz, 1H), 2.22–2.14 (m, 2H),
1.39–1.28 (m, 4H), 0.90 (t, J ¼ 7.2 Hz, 3H), 0.22 (s, 9H), 0.17 (s, 9H);
13C NMR (CDCl3): d 156.0, 123.2, 109.0, 93.7, 32.3, 31.5, 22.5, 14.0,
0.2, ꢂ0.2; MS: m=z 252 (Mþ, 18), 73 (100), 57 (43). Anal. calc. for
C14H28Si2: C, 66.58; H, 11.18. Found: C, 66.29; H, 11.02%.
(Z)-1,3-Bis(trimethylsilyl)-4-phenylbut-3-en-1-yne (2b)
Oil. IR (film): n (cmꢂ1) 3058, 3026, 2959, 2898, 2118, 1717, 1557, 1490,
1
1407, 1250, 840, 759, 698; H NMR (CDCl3): d 7.76 (s, 1H), 7.31–7.21
(m, 5H), 0.22 (s, 9H), 0.09 (s, 9H); 13C NMR (CDCl3): d 152.4, 138.6,
128.4, 127.9, 127.0, 125.2, 109.3, 96.9, 0.2, ꢂ0.1; MS: m=z 272 (Mþ,
13), 91 (80), 78 (100), 77 (57), 73 (41). Anal. calc. for C16H24Si2: C,
70.51; H, 8.88. Found: C, 70.23; H, 8.62%.
(Z)-1,3-Bis(trimethylsilyl)-5-methoxylpent-3-en-1-yne (2c)
Oil. IR (film): n (cmꢂ1) 2960, 2154, 1716, 1683, 1251, 1124, 844; 1H NMR
(CDCl3): d 6.72 (t, J ¼ 6.4 Hz, 1H), 4.03 (d, J ¼ 6.4 Hz, 2H), 3.33 (s, 3H),
0.22 (s, 9H), 0.17 (s, 9H); 13C NMR (CDCl3): d 150.2, 127.4, 107.8, 96.6,
71.1, 58.1, 0.1, ꢂ0.2; MS: m=z 240 (Mþ, 11), 73 (100), 45 (56). Anal. calc.
for C12H24OSi2: C, 59.93; H, 10.06. Found: C, 59.69; H, 9.92%.
(Z)-1,3-Bis(trimethylsilyl)dec-3-en-1-yne (2d)
Oil. IR (film): n (cmꢂ1) 2959, 2930, 2121, 1712, 1580, 1456, 1406, 1249,
842, 759; 1H NMR (CDCl3): d 6.71 (t, J ¼ 7.6 Hz, 1H), 2.20–2.14

2384
X. Ye et al.
(m, 2H), 1.38–1.22 (m, 8H), 0.88 (t, J ¼ 6.8 Hz, 3H), 0.22 (s, 9H), 0.17 (s,
9H); 13C NMR (CDCl3): d 156.0, 123.2, 109.1, 93.7, 32.6, 31.7, 29.3, 29.1,
22.6, 14.1, 0.2, ꢂ0.2; MS: m=z 280 (Mþ, 21), 73 (100), 57 (54), 43 (39).
Anal. calc. for C16H32Si2: C, 68.49; H, 11.50. Found: C, 68.21; H, 11.32%.
General Procedure for the Synthesis of (Z)-3-(Trimethylsilyl)alk-
3-en-1-ynes 3a–d
A mixture of (Z)-1,3-bis(trimethylsilyl)alk-3-en-1-yne (1 mmol) and anhy-
drous KF (10 mmol) in methanol (4 mL) was heated at reflux for 5 h.
After removal of the solvent under reduced pressure, the mixture
was extracted with diethyl ether (2 ꢁ 20 mL). The ethereal solution was
washed with water (2 ꢁ 10 mL) and dried over MgSO4. The solvent was
removed under vacuum, and the residue was purified by flash chromato-
graphy on silica gel, eluting with light petroleum ether (bp 30–60ꢀC).
Data
(Z)-3-(Trimethylsilyl)oct-3-en-1-yne (3a)
Oil. IR (film): n (cmꢂ1) 3315, 2959, 2931, 2075, 1721, 1582, 1408, 1250,
1
843, 759; H NMR (CDCl3): d 6.75 (t, J ¼ 7.6 Hz, 1H), 2.93 (s, 1H),
2.22–2.16 (m, 2H), 1.38–1.29 (m, 4H), 0.90 (t, J ¼ 7.2 Hz, 3H), 0.22 (s,
9H); 13C NMR (CDCl3): d 157.0, 122.0, 87.3, 76.7, 32.2, 31.5, 22.4,
14.0, ꢂ0.2; MS: m=z 180 (Mþ, 24), 165 (100), 73 (86), 57 (65). Anal. calc.
for C11H20Si: C, 73.25; H, 11.18. Found: C, 73.39; H, 11.25%.
(Z)-3-(Trimethylsilyl)-4-phenylbut-3-en-1-yne (3b)
Oil. IR (film): n (cmꢂ1) 3307, 3062, 2957, 2070, 1706, 1562, 1490, 1406, 1250,
841, 755, 698; 1H NMR (CDCl3): d 7.79 (s, 1H), 7.31–7.21 (m, 5H), 3.13 (s,
1H), 0.07 (s, 9H); 13C NMR (CDCl3): d 153.5, 138.5, 128.4, 128.0, 127.9,
126.1, 87.6, 79.4, ꢂ0.1; MS: m=z 200 (Mþ, 27), 185 (100), 73 (58). Anal. calc.
for C13H16Si: C, 77.93; H, 8.05. Found: C, 77.70; H, 8.12%.
(Z)-3-(Trimethylsilyl)-5-methoxylpent-3-en-1-yne (3c)
1
Oil. IR (film): n (cmꢂ1) 3305, 2960, 2064, 1250, 1128, 843; H NMR
(CDCl3): d 6.30 (t, J ¼ 6.4 Hz, 1H), 4.24 (d, J ¼ 6.4 Hz, 2H), 3.37

Difunctionalized 1,3-Dienes
2385
(s, 3H), 2.97 (s, 1H), 0.17 (s, 9H); 13C NMR (CDCl3): d 148.5, 144.0, 86.8,
76.6, 72.1, 58.0, ꢂ0.1; MS: m=z 168 (Mþ, 21), 153 (83), 73 (100), 45 (48).
Anal. calc. for C9H16OSi: C, 64.22; H, 9.58. Found: C, 64.39; H, 9.62%.
(Z)-3-(Trimethylsilyl)dec-3-en-1-yne (3d)
Oil. IR (film): n (cmꢂ1) 3315, 2958, 2928, 2078, 1715, 1581, 1456, 1407,
1
1250, 843, 759; H NMR (CDCl3): d 6.73 (t, J ¼ 7.6 Hz, 1H), 2.90 (s,
1H), 2.22–2.15 (m, 2H), 1.38–1.21 (m, 8H), 0.87 (t, J ¼ 6.8 Hz, 3H),
0.21 (s, 9H); 13C NMR (CDCl3): d 157.1, 121.9, 87.3, 76.7, 32.6, 31.7,
29.3, 29.0, 22.6, 14.1, ꢂ0.2; MS: m=z 208 (Mþ, 31), 193 (100), 73 (69),
57 (46), 43 (52). Anal. calc. for C13H24Si: C, 74.92; H, 11.61. Found:
C, 74.68; H, 11.39%.
General Procedure for the Synthesis of (1E,3Z)-1-Arylseleno-
3-(trimethylsilyl)-substituted 1,3-dienes 5a–j
A dry, 10-mL, round-bottomed flask was charged with Cp2Zr(H)Cl
(1.05 mmol) under Ar. THF (4 mL) was injected, followed by addition
of (Z)-3-(trimethylsilyl)alk-3-en-1-yne 3 (1 mmol). The mixture was stir-
red for 40 min at room temperature to yield a clear solution. A solution
of ArSeBr (1.05 mmol) in THF (3 mL) was then added, and stirred at
room temperature for 1 h. The mixture was diluted with diethyl ether
(30 mL), and the mixture was filtered through a short plug of silica gel
and concentrated to give a residue. The residue was purified by prepara-
tive thin-layer chromatography (TLC) on silica gel, eluting with light
petroleum ether (bp 30–60ꢀC).
Data
(1E,3Z)-1-Phenylseleno-3-(trimethylsilyl)-1,3-octadiene (5a)
Oil. IR (film): n (cmꢂ1) 3072, 2956, 2927, 1712, 1579, 1477, 1249, 951, 837,
1
734; H NMR (CDCl3): d 7.47–7.25 (m, 5H), 6.96 (d, J ¼ 16 Hz, 1H),
6.58 (d, J ¼ 16 Hz, 1H), 5.82 (t, J ¼ 7.2 Hz, 1H), 2.22–2.15 (m, 2H),
1.39–1.24 (m, 4H), 0.89 (t, J ¼ 7.2 Hz, 3H), 0.15 (s, 9H); 13C NMR
(CDCl3): d 143.6, 138.0, 136.8, 131.5, 131.3, 129.3, 126.8, 118.9, 31.6,
28.9, 22.5, 14.1, ꢂ0.5; MS: m=z 338 (Mþ, 94), 323 (77), 157 (51), 73 (100),
59 (62). Anal. calc. for C17H26SiSe: C, 60.50; H, 7.77. Found: C, 60.29;
H, 7.55%.

2386
X. Ye et al.
(1E,3Z)-1-(4-Chlorophenylseleno)-3-(trimethylsilyl)-1,3-octadiene (5b)
Oil. IR (film): n (cmꢂ1) 2956, 2926, 1711, 1558, 1474, 1249, 952, 837, 812;
1H NMR (CDCl3): d 7.38 (d, J ¼ 8.0 Hz, 2H), 7.25 (d, J ¼ 8.0 Hz, 2H),
6.97 (d, J ¼ 16 Hz, 1H), 6.53 (d, J ¼ 16 Hz, 1H), 5.84 (t, J ¼ 7.2 Hz, 1H),
2.20–2.16 (m, 2H), 1.39–1.25 (m, 4H), 0.90 (t, J ¼ 7.2 Hz, 3H), 0.15 (s,
9H); 13C NMR (CDCl3): d 144.1, 137.9, 137.6, 133.0, 132.7, 129.6,
129.4, 118.3, 31.6, 29.0, 22.5, 14.1, ꢂ0.5; MS: m=z 374 (Mþ, 23, 37Cl),
372 (Mþ, 61, 35Cl), 357 (37), 191 (48), 73 (100), 59 (49). Anal. calc. for
C17H25SiSeCl: C, 54.89; H, 6.77. Found: C, 54.62; H, 6.51%.
(1E,3Z)-1-(4-Methylphenylseleno)-3-(trimethylsilyl)-1,3-octadiene (5c)
1
Oil. IR (film): n (cmꢂ1) 2956, 2925, 1586, 1489, 1248, 949, 837, 801; H
NMR (CDCl3): d 7.37 (d, J ¼ 8.0 Hz, 2H), 7.11 (d, J ¼ 8.0 Hz, 2H),
6.90 (d, J ¼ 16 Hz, 1H), 6.57 (d, J ¼ 16 Hz, 1H), 5.80 (t, J ¼ 7.2 Hz, 1H),
2.33 (s, 3H), 2.21–2.15 (m, 2H), 1.38–1.24 (m, 4H), 0.89 (t, J ¼ 7.2 Hz,
3H), 0.14 (s, 9H); 13C NMR (CDCl3): d 143.2, 138.0, 137.0, 135.7,
132.0, 130.1, 127.1, 119.8, 31.6, 28.9, 22.5, 21.1, 14.0, ꢂ0.5; MS: m=z
352 (Mþ, 81), 337 (34), 172 (47), 143 (74), 91 (88), 73 (100), 59 (69).
Anal. calc. for C18H28SiSe: C, 61.51; H, 8.03. Found: C, 61.62; H, 8.23%.
(1E,3Z)-1-Phenylseleno-3-(trimethylsilyl)-4-phenyl-1,3-butadiene (5d)
1
Oil. IR (film): n (cmꢂ1) 2956, 1713, 1574, 1490, 1250, 961, 839, 734; H
NMR (CDCl3): d 7.47–7.23 (m, 10H), 7.02 (d, J ¼ 16 Hz, 1H), 6.77
(s, 1H), 6.76 (d, J ¼ 16 Hz, 1H), 0.26 (s, 9H); 13C NMR (CDCl3): d
140.5, 139.2, 137.7, 136.7, 132.3, 130.5, 129.4, 129.3, 128.1, 127.2, 127.1,
121.1, ꢂ0.4; MS: m=z 358 (Mþ, 9.4), 314 (84), 312 (77), 157 (100), 77
(67), 73 (78). Anal. calc. for C19H22SiSe: C, 63.84; H, 6.20. Found: C,
63.54; H, 6.25%.
(1E,3Z)-1-(4-Chlorophenylseleno)-3-(trimethylsilyl)-4-phenyl-1,3-
butadiene (5e)
Oil. IR (film): n (cmꢂ1) 2956, 2854, 1716, 1573, 1490, 1250, 956, 838, 813,
696; 1H NMR (CDCl3): d 7.39 (d, J ¼ 8.4 Hz, 2H), 7.35–7.23 (m, 7H), 6.98
(d, J ¼ 16 Hz, 1H), 6.79 (s, 1H), 6.70 (d, J ¼ 16 Hz, 1H), 0.25 (s, 9H);
13C NMR (CDCl3): d 140.4, 139.6, 137.6, 137.3, 133.7, 133.5, 129.4,
129.3, 128.6, 128.1, 127.3, 120.4, ꢂ0.5; MS: m=z 394 (Mþ, 25, 37Cl), 392

Difunctionalized 1,3-Dienes
2387
(Mþ, 64, 35Cl), 377 (15), 204 (65), 185 (89), 128 (81), 73 (100). Anal. calc.
for C19H21SiSeCl: C, 58.22; H, 5.40. Found: C, 58.34; H, 5.29%.
(1E,3Z)-1-(4-Methylphenylseleno)-3-(trimethylsilyl)-4-phenyl-1,3-
butadiene (5f)
Oil. IR (film): n (cmꢂ1) 2957, 2855, 1713, 1579, 1492, 1249, 957, 839, 816,
1
696; H NMR (CDCl3): d 7.40 (d, J ¼ 8.0 Hz, 2H), 7.30–7.23 (m, 7H),
6.96 (d, J ¼ 16 Hz, 1H), 6.76 (d, J ¼ 16 Hz, 1H), 6.75 (s, 1H), 2.35 (s,
1H), 0.26 (s, 9H); 13C NMR (CDCl3): d 140.5, 138.7, 137.7, 137.3,
135.6, 133.0, 132.9, 130.1, 129.4, 128.1, 127.1, 121.9, 21.1, ꢂ0.4; MS:
m=z 372 (Mþ, 21), 357 (15), 171 (56), 91 (79), 73 (100). Anal. calc. for
C20H24SiSe: C, 64.66; H, 6.51. Found: C, 64.37; H, 6.39%.
(1E,3Z)-1-Phenylseleno-3-(trimethylsilyl)-1,3-decadiene (5g)
Oil. IR (film): n (cmꢂ1) 3058, 2925, 2855, 1713, 1683, 1576, 1476, 1249,
953, 839, 735; 1H NMR (CDCl3): d 7.49–7.25 (m, 5H), 6.96 (d, J ¼ 15.6 Hz,
Hz, 1H), 6.60 (d, J ¼ 15.6 Hz, 1H), 5.83 (t, J ¼ 7.2 Hz, 1H), 2.20–2.16 (m,
2H), 1.39–1.26 (m, 8H), 0.89 (t, J ¼ 7.2 Hz, 3H), 0.16 (s, 9H); 13C NMR
(CDCl3): d 143.7, 138.1, 136.8, 131.5, 131.3, 129.2, 126.8, 118.9, 31.7,
29.4, 29.2, 29.1, 22.6, 14.1, ꢂ0.5; MS: m=z 366 (Mþ, 14), 351 (17), 157
(31), 73 (100), 59 (42). Anal. calc. for C19H30SiSe: C, 62.43; H, 8.27.
Found: C, 62.19; H, 8.35%.
(1E,3Z)-1-(4-Chlorophenylseleno)-3-(trimethylsilyl)-1,3-decadiene (5h)
Oil. IR (film): n (cmꢂ1) 2956, 2926, 2856, 1683, 1562, 1474, 1249, 954, 838,
1
813; H NMR (CDCl3): d 7.38 (d, J ¼ 8.4 Hz, 2H), 7.25 (d, J ¼ 8.4 Hz,
2H), 6.96 (d, J ¼ 16 Hz, 1H), 6.53 (d, J ¼ 16 Hz, 1H), 5.85 (t, J ¼ 7.2 Hz,
1H), 2.20–2.16 (m, 2H), 1.38–1.26 (m, 8H), 0.89 (t, J ¼ 7.2 Hz, 3H), 0.15
(s, 9H); 13C NMR (CDCl3): d 144.1, 137.9, 137.6, 133.0, 132.7, 129.6,
129.4, 118.3, 31.7, 29.4, 29.3, 29.1, 22.6, 14.1, ꢂ0.6; MS: m=z 402 (Mþ,
14, 37Cl), 400 (Mþ, 43, 35Cl), 385 (26), 191 (37), 73 (100), 59 (51). Anal.
calc. for C19H29SiSeCl: C, 57.05; H, 7.31. Found: C, 56.82; H, 7.23%.
(1E,3Z)-1-(4-Methylphenylseleno)-3-(trimethylsilyl)-1,3-decadiene (5i)
Oil. IR (film): n (cmꢂ1) 2956, 2926, 1682, 1562, 1489, 1456, 1249, 950, 839,
802; 1H NMR (CDCl3): d 7.37 (d, J ¼ 8.0 Hz, 2H), 7.11 (d, J ¼ 8.0 Hz, 2H),

2388
X. Ye et al.
6.90 (d, J¼ 15.6 Hz, 1H), 6.56 (d, J ¼ 15.6Hz, 1H), 5.80 (t, J ¼ 7.2 Hz, 1H),
2.33 (s, 3H), 2.20–2.14 (m, 2H), 1.38–1.26 (m, 8H), 0.89 (t, J ¼ 7.2 Hz, 3H),
0.14 (s, 9H); 13C NMR (CDCl3): d 143.2, 138.1, 136.9, 135.8, 132.0, 130.0,
127.1, 119.7, 31.7, 29.4, 29.2, 29.1, 22.6, 21.1, 14.1, ꢂ0.6; MS: m=z 380
(Mþ, 31), 365 (28), 91 (76), 73 (100), 59 (57). Anal. calc. for C20H32SiSe:
C, 63.29; H, 8.50. Found: C, 63.52; H, 8.43%.
(1E,3Z)-1-Phenylseleno-3-(trimethylsilyl)-5-methoxy-1,3-pentadiene (5j)
Oil. IR (film): n (cmꢂ1) 3057, 2961, 1682, 1594, 1249, 1123, 954, 843, 734;
1H NMR (CDCl3): d 7.48–7.24 (m, 5H), 6.94 (d, J ¼ 15.6 Hz, 1H), 6.56
(d, J ¼ 15.6 Hz, 1H), 6.45 (t, J ¼ 6.4 Hz, 1H), 4.07 (d, J ¼ 6.4 Hz, 2H),
3.38 (s, 3H), 0.24 (s, 9H); 13C NMR (CDCl3): d 149.8, 138.3, 136.9,
131.4, 131.1, 129.2, 127.6, 118.5, 71.2, 58.4, ꢂ0.1; MS: m=z 326 (Mþ, 23),
311 (29), 157 (33), 73 (100), 45 (62). Anal. calc. for C15H22OSiSe: C,
55.36; H, 6.81. Found: C, 55.13; H, 6.65%.
Synthesis of (1E,3Z)-1-Phenyl-3-(trimethylsilyl)-1,3-octadiene 6
PhMgBr (2.5 mmol) in diethyl ether (4 mL) was added to a mixture of
(1E,3Z)-1-phenylseleno-3-(trimethylsilyl)-1,3-octadiene 5a (1 mmol) and
NiCl2(dppp) (0.03 mmol) in diethyl ether (8 mL) under Ar at room
temperature with stirring. The resulting mixture was heated to reflux for
10 h. The mixture was treated with sat. NH4Cl aq. solution (15 mL) at
0ꢀC and extracted with diethyl ether (2 ꢁ 20 mL). The ethereal solution
was washed with water (2 ꢁ 20 mL) and dried (MgSO4). Removal of the
solvent under reduced pressure gave an oil, which was purified by prepara-
tive TLC on silica gel, eluting with light petroleum ether (bp 30–60ꢀC). Oil.
IR (film): n (cmꢂ1) 3059, 3024, 2958, 1620, 1590, 1491, 1249, 962, 841, 745;
1H NMR (CDCl3): d 7.46–7.18 (m, 5H), 6.84 (d, J ¼ 16.2 Hz, 1H), 6.51 (d,
J ¼ 16.2 Hz, 1H), 6.41 (t, J ¼ 7.0 Hz, 1H), 2.29–2.20 (m, 2H), 1.42–1.20 (m,
4H), 0.89 (t, J ¼ 7.2 Hz, 3H), 0.16 (s, 9H); 13C NMR (CDCl3): d 145.4,
138.2, 134.9, 128.7, 128.5, 127.2, 126.6, 126.1, 32.2, 31.9, 22.5, 14.0, 0.6;
MS: m=z 258 (Mþ, 12), 243 (26), 77 (38), 73 (100), 57 (42). Anal. calc.
for C17H26Si: C, 78.99; H, 10.14. Found: C, 78.73; H, 9.95%.
CONCLUSION
In conclusion, we have developed a highly stereoselective and general
route to difunctionalized 1,3-dienes containing silicon and selenium by
hydrozirconation of (Z)-3-(trimethylsilyl)alk-3-en-1-ynes, followed by

Difunctionalized 1,3-Dienes
2389
trapping with arylselenenyl bromides. The present method has the advan-
tages of readily available starting materials, straightforward and simple
procedures, mild reaction conditions, good stereoselectivity, and good
yields. Investigations into the synthetic applications of compounds 5
are currently in progress.
ACKNOWLEDGMENTS
We thank the National Natural Science Foundation of China (Project
No. 20462002) and the Natural Science Foundation of Jiangxi Province
(Project No. 2007GZW0172) for financial support.
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