A general approach to difunctionalised 1,3-dienes containing silicon and halogen via hydrozirconation of (Z)-3-(trimethylsilyl)alk-3-en-1-ynes

Article abstract of DOI:10.3184/030823407X218039

Sonogashira coupling of (E)-α-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 high yields. (1E,3Z)-1-Halo-3-

Full text of DOI:10.3184/030823407X218039

JOURNAL OF CHEMICAL RESEARCH 2007
JUNE, 319–322
RESEARCH PAPER 319
A general approach to difunctionalised 1,3-dienes containing silicon and
halogen via hydrozirconation of (Z)-3-(trimethylsilyl)alk-3-en-1-ynes
Xinglin Yea,b, Pingping Wangb and Mingzhong Caia*
aDepartment of Chemistry, Jiangxi Normal University, Nanchang 330022, P. R. China
bDepartment of Chemistry, Jiujiang University, Jiujiang 332000, P. R. China
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 desilylation reaction to afford (Z)-3-(trimethylsilyl)alk-3-en-1-ynes 3 in high yields.
(1E,3Z)-1-Halo-3-(trimethylsilyl)-substituted 1,3-dienes 5 could be synthesised stereoselectively via hydrozirconation
of (Z)-3-(trimethylsilyl)alk-3-en-1-ynes 3, followed by trapping with iodine or N-bromosuccinimide.
Keywords: difunctionalised 1,3-diene, Sonogashira coupling, hydrozirconation, vinylsilane, vinylic iodide
The stereocontrolled synthesis of 1,3-dienes containing metal
or heteroatom functional groups has been of considerable
interest in organic synthesis because many useful functional
group transformations can be achieved by the introduction
and removal of metal or heteroatom functionalities.
The stereoselective synthesis of 1,3-dienyl sulfides,1 1,3-
dienyl selenides,2 1,3-dienylsilanes3 and 1,3-dienylstannanes4
has already been described in the literature. Recently, the
synthesis of difunctionalised 1,3-dienes has also attracted much
attention since such dienes may find use as synthetic building
blocks.5 In addition, difunctionalised 1,3-dienes containing
heteroatom can control both regio- and stereoselectivity
and play a very important role in cycloadditions.6 Jin and
co-workers reported the stereoselective synthesis of 2-alkoxy-
3-alkyl(aryl)thiobuta-1,3-dienes by Negishi coupling between
α-alkyl(aryl)thio vinyl zinc chloride and α-bromo vinyl ether.7
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.8
The stereoselective synthesis of 1,4-dihalo-1,3-dienes has
also been described.9 Very recently, we have 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)-α-
iodovinylstannanes in the presence of Pd(PPh3)4 catalyst.10
However, to the best of our knowledge, there is no well-
established method for the preparation of stereoselectively
difunctionalised 1,3-dienes containing silicon and halogen.
Herein, we report that (1E,3Z)-1-halo-3-(trimethylsilyl)-
substituted 1,3-dienes can be conveniently synthesised via
hydrozirconation of (Z)-3-(trimethylsilyl)alk-3-en-1-ynes,
followed by trapping with iodine or N-bromosuccnimide
(NBS).
and histrionicotoxin.14 Very recently, Hoshi et al.15
reported the synthesis of terminal conjugated enynes via
Cu-mediated Suzuki-Miyaura cross-coupling reactions of
alkenyldialkylboranes with (trimethylsilyl)ethynyl bromide.
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 prepared according to Scheme 1.
Sonogashira coupling of alkenyl iodides with terminal
alkynes provides a simple and general route for the
synthesis of conjugated enynes.16 We observed that, when
the coupling reactions of (E)-α-iodovinylsilanes 1 with
(trimethylsilyl)acetylene were performed in piperidine at
room temperature using Pd(PPh3)4 and CuI as co-catalysts,
fairly rapid reactions occurred affording stereoselectively
the desired (Z)-1,3-bis(trimethylsilyl)alk-3-en-1-ynes 2 in
high yields, the typical results are summarised in Table 1.
Kusumoto et al.17 reported that the desilylation reaction
of (E)-1,2,4-tri(trimethylsilyl)but-1-en-3-yne with KF in
methanol afforded (E)-1,2-bis-(trimethylsilyl)but-1-en-3-yne,
the desilylation reaction occurring selectively at the acetylenic
carbon atom. We investigated the desilylation reaction of
(Z)-1,3-bis(trimethylsilyl)alk-3-en-1-ynes
2 with KF in
methanol in order to prepare (Z)-3-(trimethylsilyl)alk-3-en-
1-ynes 3. We found that the desilylation reaction of
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
2a
2b
2c
2d
3a
3b
3c
3d
87
90
85
88
86
87
81
84
Ph
CH3OCH2
n-C6H13
n-Bu
Ph
CH3OCH2
n-C6H13
There has been a lively interest in terminal conjugated
enynes, alk-3-en-1-ynes, due to 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
because the terminal conjugated enyne unit occurs in natural
products such as laurencn,11 dactylyne,12 quinolizidine,13
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 (3 ml) at 70°C for 5 h.
cIsolated yield of 2 based on the 1 used.
SiMe3
R
H
SiMe3
I
R
H
SiMe3
R
H
Pd(PPh ) /CuI
3 4
Piperidine, r.t.
KF
MeOH
Me3Si
+
SiMe3
2
1
3
Scheme 1
* Correspondent. E-mail: caimzhong@163.com
PAPER: 07/4636

320 JOURNAL OF CHEMICAL RESEARCH 2007
SiMe3
R
SiMe3
R
H
SiMe3
R
H
H
Cp2Zr(H)Cl
THF, r.t.
H
X
I2 or NBS
THF, r.t.
H
ZrCp2Cl
H
H
4
3
5
Scheme 2
Table
2 Synthesis of (1E,3Z)-1-halo-3-(trimethylsilyl)-sub-
(Z)-1,3-bis(trimethylsilyl)alk-3-en-1-ynes
2
with
KF
stituted 1,3-dienes 5
proceeded smoothly in methanol at 70°C to give the desired
(Z)-3-(trimethylsilyl)alk-3-en-1-ynes 3 in high yields. Typical
results are also summarised in Table 1.
Entry
R
X
Product
Yielda/%
1
2
3
4
5
6
n-C4H9
n-C4H9
Ph
I
Br
I
Br
I
Br
5a
5b
5c
5d
5e
5f
74
76
78
80
73
81
Hydrozirconation has emerged as a unique hydrometallation
with some attractive features such as the high regioselectivity
and stereoselectivity observed with alkynes18 and heteroatom-
substituted alkynes.19 However, the hydrozirconation of
terminal conjugated enynes has received less attention.20
With a convenient route to (Z)-3-(trimethylsilyl)alk-3-en-1-ynes
3 established we decded to investigate the feasibility 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 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 iodine or NBS to give
stereoselectively (1E,3Z)-1-halo-3-(trimethylsilyl)-substituted
1,3-dienes 5 in good yields (Scheme 2). Typical results are
summarised in Table 2. As shown in Table 2, a variety of
(1E,3Z)-1-halo-3-(trimethylsilyl)-substituted1,3-dienes 5 could
be synthesised stereoselectively via hydrozirconation of
(Z)-3-(trimethylsilyl)alk-3-en-1-ynes 3, followed by trapping
with iodine or NBS. The (1E)-configuration of compounds
Ph
n-C6H13
n-C6H13
aIsolated yield based on the 3 used.
Investigations into the synthetic applications of compounds 5
are currently in progress.
Experimental
1H NMR spectra were recorded on a Bruker AC-P400 (400 MHz)
spectrometer with 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.
IR spectra were determined on an FTS-185 instrument as neat films.
Mass spectra were obtained on a Finigan 8239 mass spectrometer.
Microanalyses were measured using
a Yanaco MT-3 CHN
microelemental analyser. All reactions were carried out in pre-
dried glassware (150°C, 4 h) and cooled under a stream of dry Ar.
All solvents were dried, deoxygenated and freshly distilled before
use. (E)-α-Iodovinylsilanes 1 were prepared from alkynylsilanes
according to a literature procedure.21
1
5a–f has been proved by their H NMR spectra which show
two doublets at δ = 6.03–7.47 with coupling constants of 13.6–
15.2 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 compound 5a was
confirmed by NOESY experiments. An enhancement of
the allylic protons was observed as the vinylic proton
(δ = 6.17 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
(δ = 6.17 ppm) and one other vinylic proton (δ = 6.03 ppm)
was also observed. The NOE results indicate that 5a has the
expected (1E,3Z)-configuration.
We have also carried out the palladium-catalysed cross-
coupling reaction of compound 5a with phenylmagnesium
bromideinTHFtoaffordiodine-free(1Z,3E)-2-(trimethylsilyl)-
substituted 1,3-diene 6 in 87% yield (Scheme 3).
In summary, we have developed a highly stereoselective and
general route to difunctionalised 1,3-dienes containing silicon
and halogen by hydrozirconation of (Z)-3-(trimethylsilyl)alk-
3-en-1-ynes, followed by trapping with iodine or NBS. The
present method has the advantages of readily available starting
materials, straightforward and simple procedures, mild
reaction conditions, high stereoselectivity and good yields.
General procedure for the synthesis of (Z)-1,3-bis(trimethylsilyl)alk-
3-en-1-ynes 2a–d
(E)-α-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
resulting mixture was stirred at room temperature for 5 min. To this
solution was added (trimethylsilyl)acetylene (3.0 mmol), and the
reaction mixture was stirred at room temperature for 2 h, quenched
with sat. NH4Cl aq. solution (10 ml) at 0°C 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 reduced
pressure and the residue was purified by flash chromatography on
silica gel eluting with light petroleum ether (bp. 30–60°C).
(Z)-1,3-Bis(trimethylsilyl)oct-3-en-1-yne (2a): Oil. IR (film):
ν (cm-1) 2959, 2928, 2120, 1719, 1581, 1406, 1249, 841, 759;
1H NMR (CDCl3): δ 6.71 (t, J = 7.6 Hz, 1H), 2.22–2.14 (m, 2H),
1.39–1.28 (m, 4H), 0.90 (t, J = 7.2 Hz, 3H), 0.22 (s, 9H), 0.17
(s, 9H); 13C NMR (CDCl3): δ 156.0, 123.2, 109.0, 93.7, 32.3, 31.5,
22.5, 14.0, 0.2, –0.2; MS: m/z 252 (M+, 18), 73 (100), 57 (43); Anal.
Calc. for C14H28Si2: C, 66.58; H, 11.18. Found: C, 66.3; H, 11.0%.
(Z)-1,3-Bis(trimethylsilyl)-4-phenylbut-3-en-1-yne
(2b):
Oil.
IR (film): ν (cm-1) 3058, 3026, 2959, 2898, 2118, 1717, 1557,
1
1490, 1407, 1250, 840, 759, 698; H NMR (CDCl3): δ 7.76 (s, 1H),
7.31–7.21 (m, 5H), 0.22 (s, 9H), 0.09 (s, 9H); 13C NMR (CDCl3):
δ 152.4, 138.6, 128.4, 127.9, 127.0, 125.2, 109.3, 96.9, 0.2, –0.1;
MS: m/z 272 (M+, 13), 91 (80), 78 (100), 77 (57), 73 (41); Anal. Calc.
for C16H24Si2: C, 70.51; H, 8.88. Found: C, 70.2; H, 8.6%.
n-C4H9
SiMe3
n-C4H9
SiMe3
H
Pd(PPh3)4
H
I
+
PhMgBr
H
H
THF, rt, 24 h
H
Ph
H
6
5a
Yield: 87%
Scheme 3
PAPER: 07/4636

JOURNAL OF CHEMICAL RESEARCH 2007 321
(Z)-1,3-Bis(trimethylsilyl)-5-methoxypent-3-en-1-yne (2c): Oil.
IR (film): ν (cm-1) 2960, 2154, 1716, 1683, 1251, 1124, 844; 1H NMR
(CDCl3): δ 6.72 (t, J = 6.4 Hz, 1H), 4.03 (d, J = 6.4 Hz, 2H), 3.33
(s, 3H), 0.22 (s, 9H), 0.17 (s, 9H); 13C NMR (CDCl3): δ 150.2, 127.4,
107.8, 96.6, 71.1, 58.1, 0.1, –0.2; MS: m/z 240 (M+, 11), 73 (100),
45 (56); Anal. Calc. for C12H24OSi2: C, 59.93; H, 10.06. Found: C,
59.7; H, 9.9%.
(m, 4H), 0.90 (t, J = 7.2 Hz, 3H), 0.17 (s, 9H); 13C NMR (CDCl3):
δ 146.3, 142.7, 137.6, 102.6, 31.9, 31.8, 22.5, 14.1, 0.27; MS: m/z
261 (M+, 1.2), 85 (68), 73 (100), 57 (79); Anal. Calc. for C11H21SiBr:
C, 50.55; H, 8.10. Found: C, 50.3; H, 8.2%.
(1E,3Z)-1-Iodo-3-(trimethylsilyl)-4-phenyl-1,3-butadiene (5c): Oil.
IR (film): ν (cm-1) 3025, 3064, 2955, 2897, 1714, 1590, 1492, 1249,
1
940, 840, 774, 697; H NMR (CDCl3): δ 7.47 (d, J = 15.2 Hz, 1H),
(Z)-1,3-Bis(trimethylsilyl)dec-3-en-1-yne (2d): Oil. IR (film):
ν (cm-1) 2959, 2930, 2121, 1712, 1580, 1456, 1406, 1249, 842, 759;
1H NMR (CDCl3): δ 6.71 (t, J = 7.6 Hz, 1H), 2.20–2.14 (m, 2H),
1.38–1.22 (m, 8H), 0.88 (t, J = 6.8 Hz, 3H), 0.22 (s, 9H), 0.17 (s,
9H); 13C NMR (CDCl3): δ 156.0, 123.2, 109.1, 93.7, 32.6, 31.7, 29.3,
29.1, 22.6, 14.1, 0.2, –0.2; MS: m/z 280 (M+, 21), 73 (100), 57 (54),
43 (39); Anal. Calc. for C16H32Si2: C, 68.49; H, 11.50. Found: C,
68.2; H, 11.3%.
7.39–7.26 (m, 5H), 6.77 (s, 1H), 6.38 (d, J = 15.2 Hz, 1H), 0.25 (s,
9H); 13C NMR (CDCl3): δ 145.8, 141.6, 140.0, 137.4, 129.6, 129.5,
128.3, 127.6, –0.65; MS: m/z 328 (M+, 2.1), 77 (34), 73 (100); Anal.
Calc. for C13H17SiI: C, 47.55; H, 5.22. Found: C, 47.3; H, 5.0%.
(1E,3Z)-1-Bromo-3-(trimethylsilyl)-4-phenyl-1,3-butadiene (5d):
Oil. IR (film): ν (cm-1) 3024, 3064, 2955, 1713, 1586, 1490, 1249,
937, 839, 774; 1H NMR (CDCl3): δ 7.35–7.20 (m, 6H), 6.95 (d,
J = 13.6 Hz, 1H), 6.28 (d, J = 13.6 Hz, 1H), 0.01 (s, 9H); 13C NMR
(CDCl3): δ 143.5, 142.6, 141.6, 139.2, 128.7, 127.9, 127.6, 104.5,
0.29; MS: m/z 281 (M+, 1.1), 77 (57), 73 (100); Anal. Calc. for
C13H17SiBr: C, 55.50; H, 6.09. Found: C, 55.2; H, 6.15%.
(1E,3Z)-1-Iodo-3-(trimethylsilyl)-1,3-decadiene (5e): Oil. IR
(film): ν (cm-1) 2955, 2925, 2856, 1716, 1594, 1456, 1249, 944,
839; 1H NMR (CDCl3): δ 7.04 (d, J = 14.2 Hz, 1H), 6.16 (t, J = 7.6
Hz, 1H), 6.03 (d, J = 14.2 Hz, 1H), 2.16–2.09 (m, 2H), 1.40–1.26
(m, 8H), 0.89 (t, J = 7.2 Hz, 3H), 0.17 (s, 9H); 13C NMR (CDCl3):
δ 150.7, 148.6, 146.4, 140.3, 32.0, 31.8, 29.7, 29.1, 22.6, 14.1, 0.26;
MS: m/z 336 (M+, 1.5), 127 (45), 73 (100); Anal. Calc. for C13H25SiI:
C, 46.41; H, 7.49. Found: C, 46.1; H, 7.3%.
(1E,3Z)-1-Bromo-3-(trimethylsilyl)-1,3-decadiene (5f): Oil. IR
(film): ν (cm-1) 2957, 2927, 2856, 1729, 1595, 1458, 1250, 937, 839;
1H NMR (CDCl3): δ 6.73 (d, J = 13.6 Hz, 1H), 6.17 (t, J = 7.6 Hz,
1H), 6.05 (d, J = 13.6 Hz, 1H), 2.16–2.10 (m, 2H), 1.39–1.26 (m, 8H),
0.89 (t, J = 7.2 Hz, 3H), 0.18 (s, 9H); 13C NMR (CDCl3): δ 146.1,
142.4, 137.2, 102.3, 31.8, 31.5, 29.5, 28.8, 22.4, 13.8, 0.01; MS: m/z
289 (M+, 1.1), 149 (54), 73 (100); Anal. Calc. for C13H25SiBr: C,
53.95; H, 8.71. Found: C, 53.7; H, 8.6%.
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
anhydrous 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 chromatography on silica gel eluting with light petroleum
ether (b.p. 30–60°C).
(Z)-3-(Trimethylsilyl)oct-3-en-1-yne (3a): Oil. IR (film): ν (cm-1)
3315, 2959, 2931, 2075, 1721, 1582, 1408, 1250, 843, 759; 1H NMR
(CDCl3): δ 6.75 (t, J = 7.6 Hz, 1H), 2.93 (s, 1H), 2.22–2.16 (m, 2H),
1.38–1.29 (m, 4H), 0.90 (t, J = 7.2 Hz, 3H), 0.22 (s, 9H); 13C NMR
(CDCl3): δ 157.0, 122.0, 87.3, 76.7, 32.2, 31.5, 22.4, 14.0, –0.2;
MS: m/z 180 (M+, 24), 165 (100), 73 (86), 57 (65); Anal. Calc. for
C11H20Si: C, 73.25; H, 11.18. Found: C, 73.4; H, 11.25%.
(Z)-3-(Trimethylsilyl)-4-phenylbut-3-en-1-yne (3b): Oil. IR (film):
ν (cm-1) 3307, 3062, 2957, 2070, 1706, 1562, 1490, 1406, 1250, 841,
755, 698; 1H NMR (CDCl3): δ 7.79 (s, 1H), 7.31–7.21 (m, 5H), 3.13
(s, 1H), 0.07 (s, 9H); 13C NMR (CDCl3): δ 153.5, 138.5, 128.4, 128.0,
127.9, 126.1, 87.6, 79.4, –0.1; MS: m/z 200 (M+, 27), 185 (100), 73
(58); Anal. Calc. for C13H16Si: C, 77.93; H, 8.05. Found: C, 77.7; H,
8.1%.
(Z)-3-(Trimethylsilyl)-5-methoxypent-3-en-1-yne (3c): Oil. IR (film):
ν (cm-1) 3305, 2960, 2064, 1250, 1128, 843; 1H NMR (CDCl3): δ 6.30
(t, J = 6.4 Hz, 1H), 4.24 (d, J = 6.4 Hz, 2H), 3.37 (s, 3H), 2.97 (s, 1H),
0.17 (s, 9H); 13C NMR (CDCl3): δ 148.5, 144.0, 86.8, 76.6, 72.1, 58.0,
–0.1; MS: m/z 168 (M+, 21), 153 (83), 73 (100), 45 (48); Anal. Calc.
for C9H16OSi: C, 64.22; H, 9.58. Found: C, 64.4; H, 9.6%.
(Z)-3-(Trimethylsilyl)dec-3-en-1-yne (3d): Oil. IR (film): ν (cm-1)
3315, 2958, 2928, 2078, 1715, 1581, 1456, 1407, 1250, 843, 759; 1H
NMR (CDCl3): δ 6.73 (t, J = 7.6 Hz, 1H), 2.90 (s, 1H), 2.22–2.15
(m, 2H), 1.38–1.21 (m, 8H), 0.87 (t, J = 6.8 Hz, 3H), 0.21 (s, 9H);
13C NMR (CDCl3): δ 157.1, 121.9, 87.3, 76.7, 32.6, 31.7, 29.3, 29.0,
22.6, 14.1, –0.2; MS: m/z 208 (M+, 31), 193 (100), 73 (69), 57 (46),
43 (52); Anal. Calc. for C13H24Si: C, 74.92; H, 11.61. Found: C, 74.7;
H, 11.4%.
Synthesis of (1E,3Z)-1-phenyl-3-(trimethylsilyl)-1,3-octadiene 6
To
a mixture of (1E,3Z)-1-iodo-3-(trimethylsilyl)-1,3-octadiene
5a (1.0 mmol) and Pd(PPh3)4 (0.05 mmol) in THF (2 ml) was
added a solution of Ph MgBr (1.5 mmol) in THF (3 ml) under Ar
at room temperature. The resulting mixture was stirred for 14 h at
room temperature. The mixture was treated with sat. NH4Cl aq.
solution (20 ml) at 0°C 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 preparative TLC on silica gel eluting with light
petroleum ether (b.p. 30–60°C). IR (film): ν (cm-1) 3059, 3024, 2958,
1
1620, 1590, 1491, 1249, 962, 841, 745; H NMR (CDCl3): δ 7.46–
7.18 (m, 5H), 6.84 (d, J = 16.2 Hz, 1H), 6.51 (d, J = 16.2 Hz, 1H),
6.41 (t, J = 7.0 Hz, 1H), 2.29–2.20 (m, 2H), 1.42–1.20 (m, 4H), 0.89
(t, J = 7.2 Hz, 3H), 0.16 (s, 9H); 13C NMR (CDCl3): δ 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 (M+, 12), 243 (26), 77 (38), 73 (100), 57 (42); Anal.
Calc. for C17H26Si: C, 78.99; H, 10.14. Found: C, 78.7; H, 9.95%.
General procedure for the synthesis of (1E,3Z)-1-halo-3-
(trimethylsilyl)-substituted 1,3-dienes 5a–f
We thank the National Natural Scence Foundation of China
(Project No. 20462002) and the Natural Scence Foundation of
Jiangxi Province (Project No. 0420015) for financal support.
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 stirred for 40 min at room temperature to yield a clear solution.
Iodine or NBS (1.0 mmol) was then added and the mixture was
stirred at room temperature for 30 min. After dilution with diethyl
ether (30 ml) the mixture was filtered through a short plug of silica
gel and concentrated to give a residue. The residue was purified by
preparative TLC on silica gel eluting with light petroleum ether
(b.p. 30–60°C).
(1E,3Z)-1-Iodo-3-(trimethylsilyl)-1,3-octadiene(5a): Oil. IR (film):
ν (cm-1) 2957, 2926, 1727, 1594, 1455, 1249, 946, 839, 763; 1H NMR
(CDCl3): δ 7.04 (d, J = 14.2 Hz, 1H), 6.17 (t, J = 7.6 Hz, 1H), 6.03
(d, J = 14.2 Hz, 1H), 2.18–2.10 (m, 2H), 1.39–1.26 (m, 4H), 0.91
(t, J = 7.2 Hz, 3H), 0.18 (s, 9H); 13C NMR (CDCl3): δ 150.7, 148.8,
146.4, 140.3, 31.9, 31.7, 22.4, 14.1, 0.25; MS: m/z 308 (M+, 1.4), 73
(84), 57 (100); Anal. Calc. for C11H21SiI: C, 42.84; H, 6.86. Found:
C, 42.6; H, 6.7%.
Received 8 May 2007; accepted 4 June 2007
Paper 07/4636 doi: 10.3184/030823407X218039
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