Stereoselective synthesis of 1,3-dienylstannanes by palladium catalyzed cross-coupling reactions

Article abstract of DOI:10.1016/j.jorganchem.2003.09.011

(Z)-α-Bromovinylstannanes are new difunctional group reagents, which undergo palladium catalyzed cross-coupling reactions with (E)-alkenylzirconium complexes to give stereoselectively 1,3-dienylstannanes in good yields.

Full text of DOI:10.1016/j.jorganchem.2003.09.011

Journal of Organometallic Chemistry 687 (2003) 462Á465
/
www.elsevier.com/locate/jorganchem
Stereoselective synthesis of 1,3-dienylstannanes by palladium
catalyzed cross-coupling reactions
Mingzhong Cai a,*, Hongde Ye a, Hong Zhao b, Caisheng Song a
a Department of Chemistry, Jiangxi Normal University, Nanchang 330027, People’s Republic of China
b Department of Chemistry, Shangrao Teachers’ College, Shangrao 334000, People’s Republic of China
Received 10 June 2003; received in revised form 4 September 2003; accepted 4 September 2003
Abstract
(Z)-a-Bromovinylstannanes are new difunctional group reagents, which undergo palladium catalyzed cross-coupling reactions
with (E)-alkenylzirconium complexes to give stereoselectively 1,3-dienylstannanes in good yields.
# 2003 Elsevier B.V. All rights reserved.
Keywords: Palladium; Zirconium; 1,3-Dienylstannane; Cross-coupling reaction
1. Introduction
The (E)-alkenylzirconium complexes, obtained by
hydrozirconation of 1-alkynes, can be cross-coupled
with alkenyl halides in the presence of a catalytic
amount of Pd(PPh3)4 or Ni(PPh3)4 to form 1,3-buta-
dienes [12]. In this paper, we wish to report that 1,3-
dienylstannanes could be synthesized by cross-coupling
reaction of (Z)-a-bromovinylstannanes with (E)-alke-
nylzirconium complexes in the presence of a catalytic
amount of Pd(PPh3)4.
The stereocontrolled synthesis of conjugated dienes is
of considerable interest in organic synthesis since such
dienes are often encountered in natural compounds,
such as insect sex pheromones and Achilla amide [1].
The synthesis of dienes for use in the DielsÁAlder
/
reaction is still an important challenge in organic
synthesis [2] although other elegant uses of these
compounds have been developed [3]. Conjugated dienes
are usually prepared by utilizing either a Wittig type
approach [4] or coupling reactions of stereodefined vinyl
halides with vinyl organometallic compounds catalyzed
by transition metals [5]. The synthesis of 1,3-dienes
containing functional groups is of great interest in recent
years. The stereoselective synthesis of 1,3-dienylsilanes
[6], 1,3-dienyl sulfides [7], 1,3-dienyl selenides [8] has
already been described in the literature. Dienylstannanes
serve as valuable versatile intermediates since vinylstan-
nanes are pivotal intermediates in a wide range of
2. Results and discussion
(Z)-a-Bromovinylstannanes (4) were conveniently
prepared in good yields with high stereoselectivity by
the hydrozirconation of alkynylstannanes and the
successive reaction with NBS [13]. Hydrozirconation
of 1-alkynes (1) at r.t. in THF gave (E)-alkenylzirco-
nium complexes (3), which were cross-coupled with (Z)-
a-bromovinylstannanes (4) at 40 8C in the presence of
Pd(PPh3)4 catalyst to afford 1,3-dienylstannanes (5) in
good yields (Scheme 1). The experimental results are
summarized in Table 1.
It is well documented that the cross-coupling reaction
of alkenylzirconium complexes with alkenyl halides in
the presence of a palladium catalyst occurs with reten-
tion of configuration [12]. The E-configuration of the
compounds 5 has been proved by their 1H-NMR spectra
carbonÁcarbon bond forming reactions [9]. The stereo-
/
selective synthesis of 1-stannyl-substituted 1,3-dienes
has been described in the literature [10], however, the
stereoselective synthesis of 2-stannyl-substituted 1,3-
dienes has received less attention [11].
* Corresponding author. Fax: ꢀ86-791-8517-500.
E-mail address: caimz618@sina.com (M. Cai).
/
0022-328X/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2003.09.011

M. Cai et al. / Journal of Organometallic Chemistry 687 (2003) 462Á
/465
463
Scheme 1.
3. Experimental
1H-NMR spectra were recorded on an AZ-300 (300
MHz) or a Bruker AC-P500 (500 MHz) spectrometer
with TMS as internal standard using CDCl3 as the
Table 1
Synthesis of 1,3-dienylstannanes 5aÁ
/
i
R
R1
Product 5
Yield (%) a
n-C4H9
Ph
Ph
Ph
5a
5b
5c
5d
5e
5f
78
64
58
80
72
77
76
68
71
solvent. IR spectra were determined on a PerkinÁElmer
/
683 spectrophotometer. Mass spectra were obtained on
a Finigan 8230 mass spectrometer. Microanalyses were
measured using a Yanaco MT-3 CHN microelemental
analyzer. All reactions were carried out in pre-dried
glassware (150 8C,4 h) and cooled under a stream of dry
nitrogen. Tetrahydrofuran (THF) was distilled over
sodium benzophenone ketyl immediately before use.
Cp2Zr(H)Cl was prepared according to the literature
method [16].
CH3OCH2
n-C4H9
Ph
Ph
n-C4H9
n-C4H9
n-C4H9
CH3OCH2
CH3OCH2
CH3OCH2
CH3OCH2
n-C4H9
Ph
5g
5h
5i
CH3OCH2
The products were identified by 1H-NMR, IR, MS and elemental
analyses.
a
Isolated yield.
3.1. General procedure for the synthesis of 4
which show a doublet at dꢁ
/
6.2Á
/
7.2 with a coupling
constant of 15Á16 Hz, and this is also the evidence of
/
A mixture of Cp2Zr(H)Cl (1 mmol) and alkynylstan-
nane (1 mmol) in THF (5 ml) was stirred at r.t. for 40
min to yield a clear solution. Into the resulting solution
was added NBS (1 mmol) at 0 8C, and the mixture was
stirred for 30 min, then at r.t. for 30 min. The solvent
was removed by rotary evaporator under reduced
pressure. The residue was extracted with light petroleum
the retention of the E-configuration of the starting
compounds 3. In addition, the configuration of the 1,3-
dienylstannane (5b) could be confirmed from compound
6 which was obtained by treatment of 5b with n-
butyllithium in THF followed by hydrolysis, a reaction
which occurs stereoselectively (Scheme 2) [14]. The
stereochemistry of compound 6 was easily established,
(3ꢂ10 ml) and filtered through a short plug of silica gel.
/
1
since H-NMR spectrum (500 MHz) of 6 gives rise to a
After evaporation of the filtrate, the residue was purified
by column chromatography on silica gel eluting with
light petroleum.
doubletÁ
/
doublet at dꢁ/6.97 with coupling constants of
14.7 and 9.1 Hz and a doubletÁ
/
doublet at dꢁ6.68 with
/
coupling constants of 14.6 and 9.0 Hz, which is
consistent with an (E,E)-configuration. The melting
3.1.1. (Z)-1-Bromo-1-tributylstannyl-2-phenylethene
(yield: 76%)
point of compound 6 was determined to be 148Á
/
IR (film): n (cmꢃ1) 3058, 3023, 2956, 2921, 2871,
149 8C which is also consistent with (E,E)-configuration
[15].
1
2853, 1600, 1489, 1463, 1376, 1072, 754, 722, 695; H-
In conclusion, the palladium catalyzed cross-coupling
reaction of (Z)-a-bromovinylstannanes with (E)-alke-
nylzirconium complexes provides a direct route to 1,3-
dienylstannanes (5). The method has some attractive
advantages such as mild reaction conditions, a simple
procedure and good yields. Investigations into the
synthetic applications of 1,3-dienylstannanes (5) are
currently in progress.
NMR: d 8.18 (s, 1H), 7.46Á
27H); Anal. Found: C, 50.60; H, 6.83. C20H33SnBr
Calc.: C, 50.85; H, 6.99%.
/
7.11 (m, 5H), 1.47Á0.79 (m,
/
3.1.2. (Z)-1-Bromo-1-tributylstannyl-1-hexene (yield:
83%)
IR (film): n (cmꢃ1) 2957, 2928, 2872, 2855, 1596,
1
1463, 1377, 1073, 693; H-NMR: d 6.85 (t, Jꢁ
/
7.8 Hz,
0.85 (m, 34H); Anal. Found: C,
1H), 1.97 (m, 2H), 1.67Á
/
47.54; H, 8.03. C18H37SnBr Calc.: C, 47.79; H, 8.19%.
3.1.3. (Z)-1-Bromo-1-tributylstannyl-3-methoxy-1-
propene (yield: 82%)
IR (film): n (cmꢃ1) 2957, 2922, 2872, 2853, 1606,
1
Scheme 2.
1464, 1377, 1117; H-NMR: d 7.00 (t, Jꢁ
/
6.5 Hz, 1H),

464
M. Cai et al. / Journal of Organometallic Chemistry 687 (2003) 462Á465
/
3.79 (d, Jꢁ
/
6.4 Hz, 2H), 3.33 (s, 3H), 1.65Á
/
0.76 (m,
3.2.5. (1E, 3Z)-1-Phenyl-3-tributylstannyl-1,3-
octadiene (5e)
IR (film): n (cmꢃ1) 3059, 3024, 2926, 2871, 1618,
1599, 1576, 1491, 1463, 1376, 956, 747, 691. 1H-NMR: d
27H); Anal. Found: C, 43.42; H, 7.37. C16H33OSnBr
Calc.: C, 43.64; H, 7.50%.
7.48Á
Jꢁ 7.0 Hz, 1H), 6.35 (d, Jꢁ
1.72Á
0.79 (m, 34H). MS: m/z 475 [Mꢀ, 1.6], 419 (10.6),
335 (27.5), 177 (41), 131 (88.4), 103 (59.4), 77 (73.2), 57
(100). Anal. Found: C, 65.49; H, 9.10. C26H44Sn Calc.:
C, 65.68; H, 9.26%.
/
7.21 (m, 5H), 6.94 (d, Jꢁ
/
15.8 Hz, 1H), 6.45 (t,
3.2. General procedure for the synthesis of 5aÁi
/
/
/
15.8 Hz, 1H), 2.18 (m, 2H),
/
A mixture of Cp2Zr(H)Cl (1 mmol) and alkyne (1) (1
mmol) in THF (6 ml) was stirred at r.t. for 30 min to
yield a clear solution. Into the resulting solution were
added Pd(PPh3)4 (0.05 mmol) and (Z)-a-bromovinyl-
stannane (4) (1 mmol), and the mixture was stirred at
40 8C for 24 h. The mixture was diluted with diethyl
ether (40 ml) and the mixture was filtered through a
short plug of silica gel and concentrated to give a
residue. The residue was purified by flash chromato-
graphy on silica gel eluting with light petroleum ether.
3.2.6. (2E, 4Z)-1-Methoxy-4-tributylstannyl-2,4-
nonadiene (5f)
IR (film): n (cmꢃ1) 2926, 2872, 1637, 1588, 1464,
1
1378, 1122, 962. H-NMR: d 6.40 (d, Jꢁ
/
16.1 Hz, 1H),
16.1, 7.0 Hz, 1H),
6.4 Hz, 2H), 3.31 (s, 3H), 2.09 (m, 2H),
0.81 (m, 34H). MS: m/z 444 [Mꢀ, 1.8], 387 (8.3),
6.31 (t, Jꢁ
3.92 (d, Jꢁ
1.54Á
/
7.1 Hz, 1H), 5.52 (dt, Jꢁ
/
/
3.2.1. (1Z, 3E)-1-Phenyl-2-tributylstannyl-1,3-
octadiene (5a)
/
291 (9.8), 265 (64.3), 177 (67.2), 57 (66.2), 45 (100).
Anal. Found: C, 59.37; H, 9.82. C22H44OSn Calc.: C,
59.59; H, 9.93%.
IR (film): n (cmꢃ1) 3056, 2925, 2871, 1630, 1598,
1
1489, 1463, 1376, 960, 750, 699. H-NMR: d 7.41Á
/
7.18
16.0, 7.2
0.68 (m, 34H). MS: m/z
(m, 6H), 6.43 (d, Jꢁ
/
16.0 Hz, 1H), 5.63 (dt, Jꢁ
/
Hz, 1H), 2.13 (m, 2H), 1.76Á
/
475 [Mꢀ, 1.5], 419 (23), 129 (41.7), 105 (100), 91 (63.2),
77 (78.1), 57 (63.4). Anal. Found: C, 65.42; H, 9.13.
C26H44Sn Calc.: C, 65.68; H, 9.26%.
3.2.7. (2Z, 4E)-1-Methoxy-3-tributylstannyl-2,4-
nonadiene (5g)
IR (film): n (cmꢃ1) 2925, 2871, 1594, 1464, 1376,
1116, 960. 1H-NMR: d 6.33 (t, Jꢁ
/
7.2 Hz, 1H), 6.24 (d,
15.6, 7.0 Hz, 1H), 3.92 (d,
0.82
3.2.2. (1Z, 3E)-1,4-Diphenyl-2-tributylstannyl-1,3-
butadiene (5b)
IR (film): n (cmꢃ1) 3058, 3022, 2925, 2870, 1615,
1597, 1489, 1463, 1376, 957, 744, 692. 1H-NMR: d
Jꢁ
/
15.6 Hz, 1H), 5.53 (dt, Jꢁ
/
Jꢁ
/
6.5 Hz, 2H), 3.34 (s, 3H), 2.11 (m, 2H), 1.55Á
/
(m, 34H). MS: m/z 443 [Mꢀ, 1.7], 291 (10.4), 265 (53.2),
177 (56.4), 151 (34.7), 57 (62.3), 45 (100). Anal. Found:
C, 59.41; H, 9.80. C22H44OSn Calc.: C, 59.59; H, 9.93%.
7.46Á
/
7.19 (m, 11H), 7.15 (d, Jꢁ/15.6 Hz, 1H), 6.54 (d,
Jꢁ 15.6 Hz, 1H), 1.71Á
/
/
0.77 (m, 27H). MS: m/z 496
[Mꢀ, 1.4], 439 (5.4), 207 (18.3), 206 (100), 128 (44.9),
105 (52.7), 91 (86.3), 77 (83.5). Anal. Found: C, 67.63;
H, 8.19. C28H40Sn Calc.: C, 67.88; H, 8.08%.
3.2.8. (1E, 3Z)-1-Phenyl-3-tributylstannyl-5-methoxy-
1,3-pentadiene (5h)
IR (film): n (cmꢃ1) 3060, 3024, 2925, 1642, 1599,
1493, 1449, 1376, 1091, 958, 692. 1H-NMR: d 7.48Á
/
7.18
15.4 Hz,
6.4 Hz, 2H),
0.79 (m, 27H). MS: m/z 463 [Mꢀ,
3.2.3. (1Z, 3E)-1-Phenyl-2-tributylstannyl-5-methoxy-
1,3-pentadiene (5c)
IR (film): n (cmꢃ1) 3058, 3023, 2925, 2871, 1635,
1598, 1489, 1463, 1376, 1120, 962, 752, 699. 1H-NMR: d
(m, 5H), 7.04 (d, Jꢁ
1H), 6.42 (t, Jꢁ7.2 Hz, 1H), 4.02 (d, Jꢁ
3.38 (s, 3H), 1.51Á
/
15.4 Hz, 1H), 6.48 (d, Jꢁ
/
/
/
/
7.41Á
Jꢁ15.8, 7.1 Hz, 1H), 4.01 (d, Jꢁ
3H), 1.50Á
0.71 (m, 27H). MS: m/z 464 [Mꢀ, 2.7], 407
/
7.19 (m, 6H), 6.58 (d, Jꢁ
/
15.8 Hz, 1H), 5.72 (dt,
1.4], 407 (11.3), 291 (14.8), 265 (63.5), 177 (65.4), 115
(88.7), 77 (46.3), 45 (100). Anal. Found: C, 62.37; H,
8.52. C24H40OSn Calc.: C, 62.20; H, 8.64%.
/
/6.4 Hz, 2H), 3.36 (s,
/
(8.4), 265 (51.6), 177 (69.4), 115 (95), 77 (47), 57 (66.3),
45 (100). Anal. Found: C, 62.05; H, 8.49. C24H40OSn
Calc.: C, 62.20; H, 8.64%.
3.2.9. (2Z, 4E)-1,6-Dimethoxy-3-tributylstannyl-2,4-
hexadiene (5i)
3.2.4. (5Z, 7E)-6-Tributylstannyl-5,7-dodecadiene (5d)
IR (film): n (cmꢃ1) 3024, 2925, 2872, 1587, 1464,
IR (film): n (cmꢃ1) 2921, 2871, 1594, 1458, 1376,
1
1113, 962. H-NMR: d 6.44 (d, Jꢁ
/
16.3 Hz, 1H), 6.40
16.3, 7.0 Hz, 1H), 3.96
0.81 (m, 27H).
1
1377, 960. H-NMR: d 6.22 (m, 2H), 5.45 (dt, Jꢁ
/15.4,
(t, Jꢁ
/
7.0 Hz, 1H), 5.59 (dt, Jꢁ
(m, 4H), 3.34 (s, 3H), 3.32 (s, 3H), 1.50Á
/
7.0 Hz, 1H), 2.04 (m, 4H), 1.53Á
/
0.78 (m, 41H). MS: m/z
/
456 [Mꢀ, 1.5], 399 (38), 287 (30.1), 177 (52.8), 67 (100),
57 (66.9), 55 (92.8), 43 (72.1). Anal. Found: C, 63.44; H,
10.61. C24H48Sn Calc.: C, 63.30; H, 10.55%.
MS: m/z 432 [Mꢀ, 3.1], 375 (10.7), 291 (21.5), 265
(59.8), 177 (62.4), 45 (100). Anal. Found: C, 55.41; H,
9.12. C20H40O2Sn Calc.: C, 55.68; H, 9.28%.

M. Cai et al. / Journal of Organometallic Chemistry 687 (2003) 462Á
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465
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/
After stirring for 30 min, the mixture was hydrolyzed
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/
filtered and concentrated under vacuum. The residue
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nyl-1,3-butadiene 6 (yield: 83%) as a solid. M.p. 148Á
/
149 8C, lit. [15] m.p. 149Á
/
150 8C. IR (KBr): n (cmꢃ1
3054, 3015, 1635, 1593, 1490, 992, 739, 690. H-NMR:
)
1
[8] (a) J.V. Comasseto, C.A. Brandt, Synthesis (1987) 146.;
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7.35 (m, 6H), 6.97 (dd, Jꢁ14.7, 9.1 Hz, 2H), 6.68 (dd,
Jꢁ14.6, 9.0 Hz, 2H).
/
7.5 Hz, 4H), 7.22Á
/
/
(c) Y. Ma, X. Huang, J. Chem. Soc. Perkin Trans. 1 (1997) 2953.
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/
Acknowledgements
Project 20062002 was supported by the National
Natural Science Foundation of China and this work
was also supported by the Natural Science Foundation
of Jiangxi Province in China.
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