A facile stereoselective synthesis of difunctionalized 1,3-dienes containing tin and halogen via hydrozirconation of (Z)-3-(tributylstannyl)alk-3-en-1-ynes

Article abstract of DOI:10.1016/j.jorganchem.2008.06.002

Sonogashira coupling of (E)-α-iodovinylstannanes 1 with (trimethylsilyl)acetylene gave (Z)-1-(trimethylsilyl)-3-(tributylstannyl)alk-3-en-1-ynes 2, which underwent a desilylation reaction to afford (Z)-3-(tributylstannyl)alk-3-en-1-ynes 3 in high yields. (1E,3Z)-1-Halo-3-(tributylstannyl)-substituted 1,3-dienes 5 could be synthesized stereoselectively via hydrozirconation of (Z)-3-(tributylstannyl)alk-3-en-1-ynes 3, followed by trapping with iodine or NBS.

Full text of DOI:10.1016/j.jorganchem.2008.06.002

Journal of Organometallic Chemistry 693 (2008) 2954–2958
Contents lists available at ScienceDirect
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Note
A facile stereoselective synthesis of difunctionalized 1,3-dienes containing tin
and halogen via hydrozirconation of (Z)-3-(tributylstannyl)alk-3-en-1-ynes
a
b
Ming-Zhong Cai a, , Yue Wang , Ping-Ping Wang
*
a School of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330027, PR China
b Department of Chemistry, Jiujiang University, Jiujiang 332000, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Sonogashira coupling of (E)-a-iodovinylstannanes 1 with (trimethylsilyl)acetylene gave (Z)-1-(trimethyl-
Received 19 April 2008
Received in revised form 3 June 2008
Accepted 3 June 2008
silyl)-3-(tributylstannyl)alk-3-en-1-ynes 2, which underwent a desilylation reaction to afford (Z)-3-(trib-
utylstannyl)alk-3-en-1-ynes 3 in high yields. (1E,3Z)-1-Halo-3-(tributylstannyl)-substituted 1,3-dienes 5
could be synthesized stereoselectively via hydrozirconation of (Z)-3-(tributylstannyl)alk-3-en-1-ynes 3,
followed by trapping with iodine or NBS.
Available online 7 June 2008
Ó 2008 Elsevier B.V. All rights reserved.
Keywords:
(E)-a-Iodovinylstannane
Difunctionalized 1,3-diene
Sonogashira coupling
Hydrozirconation
Stereoselective synthesis
1. Introduction
nyl-substituted 1,3-dienes via the hydromagnesiation of alkynyl-
silanes, followed by the cross-coupling reaction with (E)-a-
The stereocontrolled synthesis of 1,3-dienes containing metal
or heteroatom functional groups is of considerable interest in or-
ganic synthesis because many useful functional group transforma-
tions can be achieved by introduction and removal of metal or
heteroatom functions. In addition, heteroatom-substituted 1,3-
dienes can control both regio- and stereoselectivity and play a very
important role in cycloadditions [1]. The stereoselective synthesis
of 1,3-dienyl sulfides [2], 1,3-dienyl selenides [3], 1,3-dienylsilanes
[4], 1,3-dienylstannanes [5], and 1,3-dienyl sulfones [6] has al-
ready been described in the literature. Recently, the synthesis of
difunctionalized 1,3-dienes has also attracted great interest in or-
ganic synthesis since such dienes may find use as synthetic build-
ing blocks [7]. The synthesis of 2,3-bisboryl-1,3-dienes [8], 1,4-
dihalo-1,3-dienes [9], 1-sulfonyl-4-phenylseleno-1,3-dienes [10],
2-sulfonyl-3-phenylseleno-1,3-dienes [11], and 1-bromo-4-phen-
ylthio-1,3-dienes [12] has been described in literature. Jin et al. re-
iodovinylstannanes in the presence of Pd(PPh3)4 catalyst [15].
However, to the best of our knowledge, no well-established meth-
od is used to prepare stereoselectively (1E,3Z)-1-halo-3-(tributyl-
stannyl)-substituted 1,3-dienes. Herein, we wish to report that
(1E,3Z)-1-halo-3-(tributylstannyl)-substituted 1,3-dienes could be
conveniently synthesized via hydrozirconation of (Z)-3-(tributyl-
stannyl)alk-3-en-1-ynes, followed by trapping with iodine or NBS.
2. Results and discussion
There has been a lively interest in terminal conjugated enynes,
alk-3-en-1-ynes, due to its synthetic utility; the acetylenic hydro-
gen can be converted into various functionalities as well as un-
dergo 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 conju-
gated enyne unit occurs in natural products such as laurencin
[16], dactylyne [17], quinolizidine [18], and histrionicotoxin
[19]. Very recently, Hoshi et al. reported the synthesis of terminal
conjugated enynes via Cu-mediated Suzuki–Miyaura cross-cou-
pling reaction of alkenyldialkylboranes with (trimethylsilyl)ethy-
nyl bromide [20]. Our methodology involves the preparation
and the reactions of the building block (Z)-3-(tributylstannyl)-
alk-3-en-1-ynes 3 which can be conveniently obtained according
to Scheme 1:
ported
alkyl(aryl)thiobuta-1,3-dienes by Negishi coupling between
kyl(aryl)thio vinyl zinc chloride and -bromo vinyl ether [13].
the
stereoselective
synthesis
of
2-alkoxy-3-
a
-al-
a
Coleman et al. 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 [14]. Very recently, we
have described the stereoselective synthesis of (Z,Z)-2-silyl-3-stan-
* Corresponding author. Fax: +86 791 8120388.
E-mail address: caimzhong@163.com (M.-Z. Cai).
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.06.002

M.-Z. Cai et al. / Journal of Organometallic Chemistry 693 (2008) 2954–2958
2955
SnBu3
R
H
SnBu3
R
H
SnBu3
R
H
Pd(PPh3)4/CuI
Piperidine, r.t.
KF
MeOH
Me Si
+
3
I
2
1
3
SiMe3
Scheme 1.
substituted 1,3-dienylzirconium(IV) complexes 4, the intermedi-
ates 4 were then trapped with iodine or NBS at 0 °C to give stere-
oselectively (1E,3Z)-1-halo-3-(tributylstannyl)-substituted 1,3-
dienes 5 in good yields (Scheme 2). The typical results are summa-
rized in Table 2. As shown in Table 2, a variety of (1E,3Z)-1-halo-3-
(tributylstannyl)-substituted 1,3-dienes 5 could be synthesized
stereoselectively via hydrozirconation of (Z)-3-(tributylstan-
nyl)alk-3-en-1-ynes 3, followed by trapping with iodine or NBS.
We found that the iododestannylation reaction did not occur due
to higher reactivity of C–Zr bond than C–Sn bond. The (1E)-config-
uration of compounds 5 has been proved by their 1H NMR spectra
which show two doublets at d = 6.02–7.18 with a coupling con-
stant of 13.6 Hz, and this also indicates that hydrozirconation of
(Z)-3-(tributylstannyl)alk-3-en-1-ynes 3 with Cp2Zr(H)Cl occurs
highly regio- and stereoselectively, affording the intermediates 4.
The (3Z)-configuration of compounds 5 was readily apparent from
the 1H NMR spectra of compounds 5 which showed a (3JSn–H) cou-
pling constant of 108 Hz, fully in accord with an Z geometry [25].
The results indicate that compounds 5 has the expected (1E,3Z)-
configuration.
Table 1
Coupling reaction of 1 with (trimethylsilyl)acetylenea and desilylation of 2b
Entry
R
Product
Yieldc (%)
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
86
91
84
87
89
89
86
87
a
The reaction of 1 (2 mmol) with (trimethylsilyl)acetylene (4 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.
b
The desilylation reaction of 2 (1 mmol) with KF (10 mmol) was performed in
methanol (4 ml) at 70 °C for 5 h.
c
Isolated yield of 2 based on the 1 used.
Sonogashira coupling of alkenyl iodides with terminal alkynes
provides a simple and general route for the synthesis of conjugated
enynes [21]. We observed that, when the coupling reactions of (E)-
We have also carried out the Ni-catalyzed cross-coupling reac-
tion of compound 5a with Gringard reagents in THF to afford 1,3-
dienylstannanes 6 in good yields. Compound 6a underwent the
cross-coupling reaction with diphenyliodonium chloride in the
presence of Pd(PPh3)4 and CuI cocatalyst in DMF to give the tin-free
1,3-diene 7 in 74% yield (Scheme 3).
a-iodovinylstannanes 1 with (trimethylsilyl)acetylene were per-
formed in piperidine at room temperature using Pd(PPh3)4 and
CuI as co-catalyst, fairly rapid reactions occurred affording stere-
oselectively the desired (Z)-1-(trimethylsilyl)-3-(tributylstan-
nyl)alk-3-en-1-ynes
2 in high yields, the typical results are
In summary, we have developed a highly stereoselective and
general route to difunctionalized 1,3-dienes containing tin and hal-
ogen by hydrozirconation of (Z)-3-(tributylstannyl)alk-3-en-1-
ynes, followed by trapping with iodine or NBS. The present method
has the advantages of readily available starting materials, straight-
forward and simple procedures, mild reaction conditions, high ste-
reoselectivity and good yields. Investigations into the synthetic
applications of compounds 5 are currently in progress.
summarized in Table 1. We next investigated the desilylation reac-
tion of (Z)-1-(trimethylsilyl)-3-(tributylstannyl)alk-3-en-1-ynes 2
with KF in methanol in order to prepare (Z)-3-(tributylstan-
nyl)alk-3-en-1-ynes 3. We found that the desilylation reaction of
(Z)-1-(trimethylsilyl)-3-(tributylstannyl)alk-3-en-1-ynes
2 with
KF proceeded smoothly in methanol at 70 °C to give the desired
(Z)-3-(tributylstannyl)alk-3-en-1-ynes 3 in high yields. The typical
results are also summarized in Table 1. The stereochemistry of
compounds 2 and 3 was readily apparent from the 1H NMR spectra
of compounds 2 and 3 which showed a (3JSn–H) coupling constant
of 102–108 Hz, fully in accord with an Z geometry.
3. 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 spec-
tra 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 microel-
emental analyzer. All reactions were carried out in pre-dried glass-
ware (150 °C, 4 h) and cooled under a stream of dry Ar. All solvents
Hydrozirconation has emerged as a unique hydrometallation
with some attractive features such as the high regioselectivity
and stereoselectivity observed with alkynes [22] and hetero-
atom-substituted alkynes [23]. However, the hydrozirconation of
terminal conjugated enynes has received less attention [24] and
the hydrozirconation of 3-stannyl-substituted terminal conjugated
enynes has not been reported. With a convenient route to (Z)-3-
(tributylstannyl)alk-3-en-1-ynes 3 we decided to establish the fea-
sibility of using 3 in 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-(tributylstannyl)-
were dried, deoxygenated and freshly distilled before use. (E)-
Iodovinylstannanes were prepared from alkynylstannanes
according to literature procedure [26].
a-
1
SnBu
SnBu
R
H
R
3H
ZrCp2Cl
3 H
X
SnBu3
R
H
I2 or NBS
THF, 0oC-r.t.
H
THF, r.t.
H
H
5
4
3
Scheme 2.

2956
M.-Z. Cai et al. / Journal of Organometallic Chemistry 693 (2008) 2954–2958
Table 2
3.1.3. (Z)-1-(Trimethylsilyl)-3-(tributylstannyl)-5-methoxylpent-3-
Synthesis of (1E,3Z)-1-halo-3-(tributylstannyl)-substituted 1,3-dienes 5
en-1-yne (2c)
(cmÀ1) 2958, 2928, 2114, 1711, 1457, 1249, 1124,
Entry
R
X
Product
Yielda (%)
IR (film):
m
3
842; 1H NMR (CDCl3): d 6.82 (t, J = 5.6 Hz, JSn–H = 108 Hz, 1H),
3.94 (d, J;= 5.6 Hz, 2H), 3.32 (s, 3H), 1.54–1.48 (m, 6H), 1.37–1.28
(m, 6H), 1.02 (t, J = 8.0 Hz, 6H), 0.93–0.88 (m, 9H), 0.17 (s, 9H);
13C NMR (CDCl3): d 148.3, 127.9, 108.9, 97.7, 73.6, 58.1, 29.1,
27.4, 13.7, 11.5, 0.2; MS: m/z 458 (M+, 2.1), 401 (94), 167 (100),
73 (62); Anal. Calc. for C21H42OSiSn: C, 55.15; H, 9.26. Found: C,
55.39; H, 9.42%.
1
2
3
4
5
6
7
8
n-C4H9
Ph
CH3OCH2
n-C6H13
n-C4H9
Ph
Br
Br
Br
Br
I
I
I
I
5a
5b
5c
5d
5e
5f
76
80
72
81
74
78
72
75
CH3OCH2
n-C6H13
5g
5h
a
Isolated yield based on the 3 used.
3.1.4. (Z)-1-(Trimethylsilyl)-3-(tributylstannyl)dec-3-en-1-yne (2d)
IR (film):
m
(cmÀ1) 2958, 2927, 2112, 1713, 1583, 1464, 1249,
3
3.1. General procedure for the synthesis of (Z)-1-(trimethylsilyl)-3-
(tributylstannyl)-alk-3-en-1-ynes 2a–d
842, 759; 1H NMR (CDCl3): d 6.77 (t, J = 7.6 Hz, JSn–H = 108 Hz,
1H), 2.10–2.02 (m, 2H), 1.55–1.49 (m, 6H), 1.37–1.25 (m, 14H),
1.04–0.87 (m, 18H), 0.18 (s, 9H); 13C NMR (CDCl3): d 154.4,
123.7, 109.7, 94.6, 35.8, 31.8, 29.5, 29.2, 29.1, 27.4, 22.7, 14.1,
13.8, 11.0, 0.3; MS: m/z 498 (M+, 2.6), 441 (100), 327 (45), 73
(42); Anal. Calc. for C25H50SiSn: C, 60.36; H, 10.13. Found: C,
60.10; H, 10.31%.
(E)-a-Iodovinylstannane 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
(4.0 mmol), and the reaction mixture was stirred at room temper-
ature for 2 h, quenched with sat. NH4Cl aq. solution (10 ml) at 0 °C
and extracted with Et2O (2 Â 25 ml). The ethereal solution was
washed with water (2 Â 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 30–60 °C).
3.2. General procedure for the synthesis of (Z)-3-(tributylstannyl)alk-
3-en-1-ynes 3a–d
A mixture of (Z)-1-(trimethylsilyl)-3-(tributylstannyl)alk-3-en-
1-yne (1 mmol), 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 Â 20 ml).
The ethereal solution was washed with water (2 Â 10 ml) and
dried over MgSO4. The solvent was removed under vacuum, and
the residue was purified by flash chromatography on silica gel elut-
ing with light petroleum ether (bp 30–60 °C).
3.1.1. (Z)-1-(Trimethylsilyl)-3-(tributylstannyl)oct-3-en-1-yne (2a)
IR (film):
m
(cmÀ1) 2959, 2928, 2111, 1714, 1584, 1464, 1249,
842, 759; 1H NMR (CDCl3): d 6.78 (t, J = 7.6 Hz, JSn–H = 108 Hz,
1H), 2.11–2.02 (m, 2H), 1.57–1.48 (m, 6H), 1.39–1.28 (m, 10H),
1.02 (t, J = 8.0 Hz, 6H), 0.92–0.85 (m, 12H), 0.17 (s, 9H); 13C NMR
(CDCl3): d 154.4, 123.8, 109.7, 94.6, 35.4, 31.7, 29.1, 27.4, 22.5,
14.0, 13.7, 11.0, 0.3; MS: m/z 470 (M+, 4.2), 291 (25), 73 (100), 57
(93); Anal. Calc. for C23H46SiSn: C, 58.85; H, 9.88. Found: C,
58.59; H, 10.02%.
3
3.2.1. (Z)-3-(Tributylstannyl)oct-3-en-1-yne (3a)
IR (film): m
(cmÀ1) 3314, 2958, 2928, 2076, 1716, 1586, 1464; 1H
NMR (CDCl3): d 6.82 (t, J = 7.2 Hz, 3JSn–H = 108 Hz, 1H), 3.07 (s, 1H),
2.12–2.03 (m, 2H), 1.55–1.48 (m, 6H), 1.39–1.30 (m, 10H), 1.03 (t,
J = 8.0 Hz, 6H), 0.93–0.88 (m, 12H); 13C NMR (CDCl3): d 155.5,
122.6, 88.2, 77.7, 35.4, 31.6, 29.0, 27.3, 22.5, 14.0, 13.7, 10.8; MS:
m/z 398 (M+, 8.8), 342 (54), 178 (100), 57 (48); Anal. Calc. for
C20H38Sn: C, 60.47; H, 9.64. Found: C, 60.21; H, 9.46%.
3.1.2. (Z)-1-(Trimethylsilyl)-3-(tributylstannyl)-4-phenylbut-3-en-1-
yne (2b)
IR (film):
m
(cmÀ1) 3058, 2957, 2925, 2104, 1638, 1558, 1489,
1249, 842, 752, 697; 1H NMR (CDCl3): d 7.84 (s, JSn–H = 104 Hz,
1H), 7.33–7.22 (m, 5H), 1.46–1.38 (m, 6H), 1.29–1.20 (m, 6H),
0.92–0.83 (m, 15H), 0.23 (s, 9H); 13C NMR (CDCl3): d 151.7,
139.9, 128.2, 127.9, 127.4, 127.2, 110.3, 98.2, 28.9, 27.2, 13.7,
11.8, 0.23; MS: m/z 490 (M+, 3.3), 433 (100), 431 (69), 291 (58),
179 (57), 73 (73); Anal. Calc. for C25H42SiSn: C, 61.36; H, 8.65.
Found: C, 61.13; H, 8.82%.
3
3.2.2. (Z)-3-(Tributylstannyl)-4-phenylbut-3-en-1-yne (3b)
IR (film):
m
(cmÀ1) 3312, 3060, 2957, 2078, 1644, 1490, 1456,
3
751, 698; 1H NMR (CDCl3): d 7.88 (s, JSn–H = 108 Hz, 1H), 7.32–
7.23 (m, 5H), 3.34 (s, 1H), 1.44–1.37 (m, 6H), 1.27–1.21 (m, 6H),
0.93–0.82 (m, 15H); 13C NMR (CDCl3): d 152.8, 139.8, 128.3,
128.0, 127.4, 127.2, 88.9, 81.1, 28.8, 27.2, 13.6, 11.6; MS: m/z 417
n-C4H9
SnBu3
n-C4H9
SnBu3
H
R
H
NiCl2(dppe)
THF, 0-25 oC, 2 h
+
RMgBr
H
H
H
H
Br
5a
6a: R = n-C4H9, yield:83%
6b: R = Ph, yield: 87%
n-C4H9
SnBu3
Ph
n-C4H9
Pd(PPh3)4/CuI
DMF, r.t.
H
H
+
Ph2ICl
H
H
H
H
n-C4H9
n-C4H9
6a
7 yield: 74%
Scheme 3.

M.-Z. Cai et al. / Journal of Organometallic Chemistry 693 (2008) 2954–2958
2957
(M+À1, 5.3), 361 (100), 177 (50); Anal. Calc. for C22H34Sn: C, 63.33;
45 (100); Anal. Calc. for C18H35OBrSn: C, 46.38; H, 7.57. Found: C,
46.11; H, 7.72%.
H, 8.21. Found: C, 63.11; H, 8.02%.
3.2.3. (Z)-3-(Tributylstannyl)-5-methoxylpent-3-en-1-yne (3c)
3.3.4. (1E,3Z)-1-Bromo-3-(tributylstannyl)-1,3-decadiene 5d
IR (film):
m
(cmÀ1) 3314, 2957, 2929, 2066, 1713, 1590, 1456,
IR (film):
m
(cmÀ1) 2919, 1683, 1576, 1464, 960, 737; 1H NMR
3
3
1124; 1H NMR (CDCl3): d 6.88 (t, J = 5.6 Hz, JSn–H = 102 Hz, 1H),
3.95 (d, J = 5.6 Hz, 2H), 3.33 (s, 3H), 3.22 (s, 1H), 1.58–1.48 (m,
6H), 1.37–1.27 (m, 6H), 1.02 (t, J = 8.0 Hz, 6H), 0.92–0.88 (m, 9H);
13C NMR (CDCl3): d 149.4, 126.8, 87.6, 80.6, 73.6, 58.2, 28.9, 27.3,
13.7, 11.4; MS: m/z 386 (M+, 4.1), 329 (65), 291 (39), 235 (64),
177 (100); Anal. Calc. for C18H34OSn: C, 56.13; H, 8.90. Found: C,
56.37; H, 9.12%.
(CDCl3): d 6.85 (d, J = 13.6 Hz, 1H), 6.27 (t, J = 7.2 Hz, JSn–H
=
108 Hz, 1H), 6.02 (d, J = 13.6 Hz, 1H), 2.07–1.98 (m, 2H), 1.60–
1.24 (m, 20H), 0.97–0.82 (m, 18H); 13C NMR (CDCl3): d 147.0,
145.3, 139.3, 103.2, 34.6, 31.8, 29.8, 29.1, 29.0, 27.3, 22.6, 14.1,
13.7, 11.0; MS: m/z 507 (M+, 1.2), 450 (78), 291 (39), 177 (100),
57 (56); Anal. Calc. for C22H43BrSn: C, 52.19; H, 8.56. Found: C,
52.41; H, 8.72%.
3.2.4. (Z)-3-(Tributylstannyl)dec-3-en-1-yne (3d)
3.3.5. (1E,3Z)-1-Iodo-3-(tributylstannyl)-1,3-octadiene 5e
IR (film):
m
(cmÀ1) 3314, 2958, 2928, 2071, 1713, 1586, 1464; 1H
IR (film): m
(cmÀ1) 2959, 2927, 1682, 1567, 1463, 962; 1H NMR
NMR (CDCl3): d 6.82 (t, J = 7.6 Hz, 3JSn–H = 108 Hz, 1H), 3.07 (s, 1H),
2.11–2.02 (m, 2H), 1.56–1.48 (m, 6H), 1.37–1.28 (m, 14H), 1.05–
0.87 (m, 18H); 13C NMR (CDCl3): d 155.5, 122.6, 88.2, 77.7, 35.7,
31.8, 29.5, 29.1, 29.0, 27.3, 22.6, 14.1, 13.7, 10.8; MS: m/z 426
(M+, 1.4), 369 (40), 363 (100), 291 (32), 177 (34); Anal. Calc. for
(CDCl3): d 6.70 (d, J = 13.6 Hz, 1H), 6.61 (d, J = 13.6 Hz, 1H), 5.92 (t,
3
J = 7.2 Hz, JSn–H = 108 Hz, 1H), 2.30–2.21 (m, 2H), 1.62–1.25 (m,
22H), 0.95–0.87 (m, 12H); 13C NMR (CDCl3): d 146.2, 142.4,
105.4, 83.8, 35.9, 30.2, 29.2, 26.6, 22.3, 13.9, 13.6, 11.4; MS: m/z
469 (M+ÀBu, 38), 291 (47), 57 (100); Anal. Calc. for C20H39SnI: C,
45.74; H, 7.49. Found: C, 45.58; H, 7.26%.
C22H42Sn: C, 62.13; H, 9.95. Found: C, 62.29; H, 10.22%.
3.3. General procedure for the synthesis of (1E,3Z)-1-halo-3-
(tributylstannyl)-substituted 1,3-dienes 5a–h
3.3.6. (1E,3Z)-1-Iodo-3-(tributylstannyl)-4-phenyl-1,3-butadiene 5f
IR (film): m
(cmÀ1) 2957, 2921, 1566, 1492, 1463, 967, 759, 690;
1H NMR (CDCl3): d 7.61–7.56 (m, 2H), 7.40–7.32 (m, 3H), 7.05 (s,
3JSn–H = 108 Hz, 1H), 6.92 (d, J = 13.6 Hz, 1H), 6.85 (d, J = 13.6 Hz,
1H), 1.68–1.59 (m, 6H), 1.45–1.26 (m, 12H), 0.95–0.92 (m, 9H);
13C NMR (CDCl3): d 149.1, 143.7, 129.1, 128.5, 128.3, 128.2,
102.6, 86.7, 29.1, 26.7, 13.6, 11.3; MS: m/z 489 (M+ÀBu, 63), 291
(43), 177 (100), 77 (61); Anal. Calc. for C22H35SnI: C, 48.47; H,
6.47. Found: C, 48.20; H, 6.60%.
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 addi-
tion of (Z)-3-(tributylstannyl)alk-3-en-1-yne 3 (1 mmol). The mix-
ture was stirred for 40 min at room temperature to yield a clear
solution. It was then added dropwise a solution of iodine or NBS
(1 mmol) in THF (2 ml) at 0 °C over 15 min 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
preparative TLC on silica gel eluting with light petroleum ether (bp
30–60 °C).
3.3.7. (1E,3Z)-1-Iodo-3-(tributylstannyl)-5-methoxy-1,3-pentadiene
5g
IR (film):
m
(cmÀ1) 2919, 2850, 1589, 1456, 1123, 961; 1H NMR
3
(CDCl3): d 7.18 (d, J = 13.6 Hz, 1H), 6.36 (t, J = 5.4 Hz, JSn–H
=
108 Hz, 1H), 6.10 (d, J = 13.6 Hz, 1H), 3.89 (d, J = 5.4 Hz, 2H), 3.33
(s, 3H), 1.54–1.41 (m, 6H), 1.39–1.26 (m, 6H), 1.05–0.85 (m,
15H); 13C NMR (CDCl3): d 152.2, 146.3, 140.5, 75.2, 73.2, 58.2,
29.1, 27.4, 13.7, 11.2; MS: m/z 514 (M+, 1.4), 457 (67), 291 (36),
45 (100); Anal. Calc. for C18H35OSnI: C, 42.14; H, 6.88. Found: C,
42.39; H, 6.97%.
3.3.1. (1E,3Z)-1-Bromo-3-(tributylstannyl)-1,3-octadiene 5a
IR (film):
(CDCl3):
m
(cmÀ1) 2957, 2925, 1577, 1464, 960; 1H NMR
3
d
6.84 (d, J = 13.6 Hz, 1H), 6.27 (t, J = 7.2 Hz, JSn–
H = 108 Hz, 1H), 6.02 (d, J = 13.6 Hz, 1H), 2.07–1.98 (m, 2H),
1.51–1.24 (m, 16H), 0.99–0.85 (m, 18H); 13C NMR (CDCl3): d
147.0, 145.3, 139.3, 103.2, 34.3, 32.0, 29.1, 27.3, 22.6, 14.1,
13.7, 11.0; MS: m/z 479 (M+, 1.6), 422 (65), 291 (43), 57 (100);
Anal. Calc. for C20H39BrSn: C, 50.23; H, 8.22. Found: C, 50.39; H,
8.41%.
3.3.8. (1E,3Z)-1-Iodo-3-(tributylstannyl)-1,3-decadiene 5h
IR (film):
m
(cmÀ1) 2955, 2926, 1683, 1464, 961; 1H NMR
(CDCl3): d 6.70 (d, J = 13.6 Hz, 1H), 6.60 (d, J = 13.6 Hz, 1H), 5.93
3
(t, J = 7.2 Hz, JSn–H = 108 Hz, 1H), 2.26–2.20 (m, 2H), 1.59–1.21
3.3.2. (1E,3Z)-1-Bromo-3-(tributylstannyl)-4-phenyl-1,3-butadiene
(m, 26H), 0.95–0.82 (m, 12H); 13C NMR (CDCl3): d 146.1, 142.5,
105.5, 83.9, 36.2, 31.7, 29.8, 29.4, 28.9, 27.5, 22.6, 14.1, 13.8,
11.2; MS: m/z 497 (M+ÀBu, 43), 291 (33), 177 (100), 57 (62); Anal.
Calc. for C22H43SnI: C, 47.77; H, 7.84. Found: C, 47.51; H, 7.62%.
5b
IR (film):
m
(cmÀ1) 2957, 2918, 1708, 1560, 1489, 1455, 961,
770, 698; 1H NMR (CDCl3): d 7.41 (s, JSn–H = 108 Hz, 1H), 7.32–
7.19 (m, 5H), 7.03 (d, J = 13.6 Hz, 1H), 6.21 (d, J = 13.6 Hz, 1H),
1.38–1.16 (m, 12H), 0.92–0.83 (m, 15H); 13C NMR (CDCl3): d
145.2, 144.4, 143.9, 140.2, 128.2, 128.0, 127.6, 105.2, 28.9, 27.2,
13.7, 11.5; MS: m/z 499 (M+, 1.3), 442 (75), 291 (54), 177 (100),
77 (52); Anal. Calc. for C22H35BrSn: C, 53.04; H, 7.08. Found: C,
53.23; H, 7.32%.
3
3.4. Synthesis of 1,3-dienylstannanes 6a–b
To a mixture of (1E,3Z)-1-bromo-3-(tributylstannyl)-1,3-octadi-
ene 5a (1 mmol) and NiCl2(dppe) (0.03 mmol) in THF (2 ml) was
added a solution of RMgBr (1.5 mmol) in THF (3 ml) under Ar at
0 °C with stirring. The resulting mixture was slowly brought to
room temperature and stirred for 2 h. The mixture was treated
with sat. NH4Cl aq. solution (15 ml) at 0 °C and extracted with
diethyl ether (2 Â 30 ml). The ethereal solution was washed with
water (2 Â 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 (bp 30–
3.3.3. (1E,3Z)-1-Bromo-3-(tributylstannyl)-5-methoxy-1,3-
pentadiene 5c
IR (film):
m
(cmÀ1) 2957, 2922, 1715, 1573, 1456, 1124, 960; 1H
3
NMR (CDCl3): d 6.87 (d, J = 13.6 Hz, 1H), 6.36 (t, J = 6.0 Hz, JSn–H
=
108 Hz, 1H), 6.11 (d, J = 13.6 Hz, 1H), 3.90 (d, J = 6.0 Hz, 2H), 3.33
(s, 3H), 1.52–1.41 (m, 6H), 1.38–1.25 (m, 6H), 1.04–0.85 (m,
15H); 13C NMR (CDCl3): d 144.4, 143.6, 140.5, 104.7, 73.3, 58.2,
29.1, 27.3, 13.7, 11.4; MS: m/z 467 (M+, 2.3), 410 (63), 291 (47),
60 °C). Compound 6a: oil. IR (film):
1589, 1464, 1378, 961; 1H NMR (CDCl3): d 6.25–6.19 (m, 2H),
m
(cmÀ1) 3024, 2925, 2872,

2958
M.-Z. Cai et al. / Journal of Organometallic Chemistry 693 (2008) 2954–2958
(e) M.C. Aversa, A. Barattucci, P. Bonaccorsi, P. Giannetto, D.N. Jones, J. Org.
Chem. 62 (1997) 4376.
[2] (a) F. Naso, Pure Appl. Chem. 60 (1988) 79;
5.46 (dt, J = 15.4, 7.2 Hz, 1H), 2.09–1.95 (m, 4H), 1.51–0.82 (m,
41H); MS: m/z 456 (M+, 1.2), 399 (46), 291 (43), 287 (33), 177
(100), 57 (72). Anal. Calc. for C24H48Sn: C, 63.31; H, 10.63. Found:
(b) W.H. Pearson, K.-C. Lin, Y.-F. Poon, J. Org. Chem. 54 (1989) 5814;
(c) P.A. Grieco, S.A. May, M.D. Kaufman, Tetrahedron Lett. 39 (1998) 7047;
(d) M. Cai, D. Wang, P. Wang, J. Organomet. Chem. 691 (2006) 737.
[3] (a) J.V. Camasseto, C.A. Brandt, Synthesis (1987) 146;
(b) L. Hevesi, B. Hermans, C. Allard, Tetrahedron Lett. 35 (1994) 6729;
(c) L.S. Zhu, Z.Z. Huang, X. Huang, Tetrahedron 52 (1996) 9819;
(d) Y. Ma, X. Huang, J. Chem. Soc., Perkin Trans. 1 (1997) 2953.
[4] (a) E. Negishi, F.T. Luo, J. Org. Chem. 48 (1983) 1560;
(b) T.-Y. Luh, K.-T. Wong, Synthesis (1993) 349;
C, 63.53; H, 10.88%. Compound 6b: oil. IR (film):
m
(cmÀ1) 3060,
3025, 2927, 2872, 1620, 1598, 1578, 1490, 1376, 957, 747, 690;
1H NMR (CDCl3): d 7.47–7.22 (m, 5H), 6.95 (d, J = 16.0 Hz, 1H),
6.46 (t, J = 7.2 Hz, 1H), 6.35 (d, J = 16.0 Hz, 1H), 2.21–2.14 (m,
2H), 1.54–0.85 (m, 34H); MS: m/z 476 (M+, 1.5), 419 (27), 362
(41), 291 (38), 177 (56), 77 (81), 57 (100). Anal. Calc. for
C26H44Sn: C, 65.70; H, 9.33. Found: C, 65.48; H, 9.40%.
(c) Z.-J. Ni, P.-F. Yang, D.K.P. Ng, Y.-L. Tzeng, T.-Y. Luh, J. Am. Chem. Soc. 112
(1990) 9356.
[5] (a) F. Suzenet, E. Blart, J.P. Quintard, Synlett (1998) 879;
(b) B.H. Lipshutz, C. Lindsley, J. Am. Chem. Soc. 119 (1997) 4555;
(c) J.F. Betzer, F. Delaloge, B. Muller, A. Pancrazi, J. Org. Chem. 62 (1997)
7768.
[6] (a) J.E. Backvall, A. Ericsson, J. Org. Chem. 59 (1994) 5850;
(b) T.G. Back, S. Collins, J. Org. Chem. 46 (1981) 3249;
(c) Y. Chen, J.B. Evarts, E. Torres, P.L. Fuchs, Org. Lett. 4 (2002) 3571.
[7] (a) K. Banert, W. Fendel, J. Schlott, Angew. Chem., Int. Ed. 37 (1998) 3289;
(b) C. Wang, Q. Song, Z. Xi, Tetrahedron 60 (2004) 5207;
(c) K. Banert, J. Schlott, Tetrahedron 56 (2000) 5413;
(d) J.W. Herndon, P.P. Patel, J. Org. Chem. 61 (1996) 4500;
(e) G. Desurmont, S. Dalton, D.M. Giolando, M. Srebnik, J. Org. Chem. 61 (1996)
7943;
3.5. Synthesis of 1,3-diene 7
1,3-Dienylstannnane 6a (1.0 mmol) and diphenyliodonium
chloride (1.0 mmol) were dissolved in DMF (10 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 24 h at room temper-
ature and monitored by TLC (SiO2) for the disappearance of the
starting 1,3-dienylstannane 6a. The reaction mixture was diluted
with diethyl ether (30 ml), filtered and then treated with 20% aque-
ous KF (10 ml) for 30 min before being dried and concentrated. The
residue was purified by column chromatography on silica gel (elu-
(f) B.H. Lipshutz, J.I. Lee, Tetrahedron Lett. 32 (1991) 7211.
[8] S. Massaki, K. Takuya, H. Tamejiro, Synlett (2001) 1006.
[9] J.-H. Li, Y. Liang, Y.-X. Xie, J. Org. Chem. 69 (2004) 8125.
[10] M. Yoshimatsu, J. Hasegawa, J. Chem. Soc., Perkin Trans. 1 (1997) 211.
[11] X. Huang, M. Xie, Org. Lett. 4 (2002) 1331.
ent: light petroleum ether). Oil. IR (film):
2958, 2872, 1600, 1575, 1494, 1466, 1379, 983, 703; 1H NMR
(CDCl3): 7.37–7.27 (m, 3H), 7.11–7.09 (m, 2H), 6.23 (d,
m
(cmÀ1) 3058, 3023,
d
[12] F. Babudri, V. Fiandanese, L. Mazzone, F. Naso, Tetrahedron Lett. 35 (1994)
8847.
J = 15.6 Hz, 1H), 5.58 (t, J = 7.6 Hz, 1H), 5.11 (dt, J = 15.6, 7.6 Hz,
1H), 2.05–2.00 (m, 2H), 1.92–1.86 (m, 2H), 1.36–1.20 (m, 8H),
0.86 (t, J = 6.8 Hz, 3H), 0.80 (t, J = 7.2 Hz, 3H); 13C NMR (CDCl3): d
141.1, 139.0, 134.2, 131.6, 131.3, 129.5, 127.9, 126.5, 32.5, 32.1,
31.6, 28.7, 22.3, 22.2, 14.0, 13.9; MS: m/z 242 (M+, 1.8), 159 (18),
105 (100), 77 (52). Anal. Calc. for C18H26: C, 89.19; H, 10.81. Found:
C, 88.97; H, 10.65%.
[13] M. Su, Y. Kang, W. Yu, Z. Hua, Z. Jin, Org. Lett. 4 (2002) 691.
[14] R.S. Coleman, M.C. Walczak, Org. Lett. 7 (2005) 2289.
[15] M.-Z. Cai, Z. Zhou, P.-P. Wang, Synthesis (2006) 789.
[16] K. Tsushima, A. Murai, Tetrahedron Lett. 33 (1992) 4345. and references cited
therein.
[17] L.-X. Gao, A. Murai, Tetrahedron Lett. 33 (1992) 4349. and references cited
therein.
[18] K.M. Maloney, R.L. Danheiser, Org. Lett. 7 (2005) 3115. and references cited
therein.
[19] (a) I.L. Karle, J. Am. Chem. Soc. 95 (1973) 4036;
(b) Y. Inubushi, T. Ibuka, Heterocycles 17 (1982) 507;
(c) G. Stork, K. Zhao, J. Am. Chem. Soc. 112 (1990) 5875.
[20] M. Hoshi, N. Kawamura, K. Shirakawa, Synthesis (2006) 1961.
[21] (a) K. Sonogashira, Y. Tohda, N. Hagihara, Tetrahedron Lett. (1975) 4467;
(b) K. Sonogashira, in: B.M. Trost, I. Fleming (Eds.), Comprehensive Organic
Synthesis, vol. 3, Pergamon Press, Oxford, 1991, pp. 521–549 (Chapter 2.4, and
references cited therein).
Acknowledgements
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.
[22] (a) J. Schwartz, J. Organomet. Chem. 1 (1976) 461;
(b) D.W. Hart, T.F. Blackburn, J. Schwartz, J. Am. Chem. Soc. 97 (1975) 679.
[23] (a) L. Deloux, M. Srebnik, J. Org. Chem. 59 (1994) 6871;
(b) M.J. Dabdoub, A.C.M. Baroni, J. Org. Chem. 65 (2000) 54;
(c) A. Arefolov, N.F. Langille, J.S. Panek, Org. Lett. 3 (2001) 3281;
(d) X. Huang, D. Duan, W. Zheng, J. Org. Chem. 68 (2003) 1958.
[24] M.D. Fryzuk, G.S. Bates, C. Stone, J. Org. Chem. 56 (1991) 7201.
[25] A.J. Leusink, H.A. Budding, J.W. Marsman, J. Organomet. Chem. 9 (1967) 285.
[26] B.H. Lipshutz, R. Keil, J.C. Barton, Tetrahedron Lett. 33 (1992) 5861.
References
[1] (a) B.M. Trost, W.C. Vladuchick, A.J. Bridges, J. Am. Chem. Soc. 102 (1980)
3554;
(b) A. Padwa, B.H. Norman, Tetrahedron Lett. 29 (1988) 2417;
(c) A. Padwa, B. Harrison, S.S. Murphree, P.E. Yeske, J. Org. Chem. 54 (1989)
4232;
(d) M. Yoshimatsu, J. Hasegawa, J. Chem. Soc., Perkin Trans. 1 (1997) 211;