Stereoselective synthesis of (Z,E)-2-phenylselenobutadienes by palladium-catalyzed cross-coupling reaction

Article abstract of DOI:10.1016/S0022-328X(03)00583-7

Hydrozirconation of 1-alkynes gives ( E )-alkenylzirconium complexes 3, which are cross-coupled with (E)-α-phenylselenovinyl bromides (4) in the presence of tetrakis (triphenylphosphine) palladium catalyst to afford (Z,E )-2-phenylselenobutadienes (5) in good yields.

Full text of DOI:10.1016/S0022-328X(03)00583-7

Journal of Organometallic Chemistry 681 (2003) 98Á101
/
www.elsevier.com/locate/jorganchem
Stereoselective synthesis of (Z,E)-2-phenylselenobutadienes by
palladium-catalyzed cross-coupling reaction
Ming-Zhong Cai *, Jia-Di Huang, Chun-Yun Peng
Department of Chemistry, Jiangxi Normal University, Nanchang 330027, China
Received 22 April 2003; received in revised form 29 May 2003; accepted 29 May 2003
Abstract
Hydrozirconation of 1-alkynes gives (E)-alkenylzirconium complexes 3, which are cross-coupled with (E)-a-phenylselenovinyl
bromides (4) in the presence of tetrakis (triphenylphosphine) palladium catalyst to afford (Z,E)-2-phenylselenobutadienes (5) in
good yields.
#
2003 Elsevier Science B.V. All rights reserved.
Keywords: Selenium; Palladium; Zirconium; Hydrozirconation; 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 catalytic amount
The stereocontrolled synthesis of conjugated dienes is
of considerable interest in organic synthesis since such
dienes are often encountered in natural compounds,
such as Achillea amide [1], and are also valuable
intermediates in the synthesis of more complex targets
of Pd(PPh ) or Ni(PPh ) to form 1,3-butadienes
3 4 3 4
[12,13]. We now wish to report that (Z,E)-2-phenylse-
lenobutadienes could be synthesized by cross-coupling
reaction of (E)-alkenylzirconium complexes with (E)-a-
phenylselenovinyl bromides in the presence of a catalytic
via DielsÁAlder reaction [2]. Conjugated dienes are
/
usually prepared by utilizing either a Wittig type
approach [3] or coupling reactions of stereodefined vinyl
halides with vinyl organometallic compounds catalyzed
by transition metals [4]. The synthesis of 1,3-dienes
containing functional groups is also of considerable
interest in recent years. The stereoselective synthesis of
amount of Pd(PPh ) .
3 4
2. Results and discussion
(
E)-a-Phenylselenovinyl bromides (4) were conveni-
(
E,E)-1-trimethylsilylbutadienes [5,6], (E,E)-1-phe-
ently synthesized in good yields with high stereoselec-
tivity by the addition of hydrogen bromide to alkynyl
phenyl selenides [14]. Hydrozirconation of 1-alkynes 1 at
room temperature (r.t.) in THF gave (E)-alkenylzirco-
nium complexes 3, which were cross-coupled with (E)-a-
phenylselenovinyl bromides (4) in the presence of
Pd(PPh ) catalyst to afford (Z,E)-2-phenylselenobuta-
nylthio-butadienes [7] has already been described in
the literature. Dienyl selenides serve as valuable versatile
intermediates since vinyl selenides are synthetically
equivalent to carbonyls and can be stereospecifically
converted to alkenes by nickel-catalyzed coupling reac-
tions with Grignard reagents [8]. In the literature, we
found the stereoselective synthesis of (E,E)-1-arylsele-
nobutadienes [9] and polysubstituted dienyl selenides
3
4
dienes (5) in good yields (Scheme 1). The experimental
results are summarized in Table 1.
[10,11]. However, the synthesis of (Z,E)-2-arylseleno-
butadienes has been rarely reported [11].
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 [12,13]. The E-configuration of the
*
E-mail address: caimz618@sina.com (M.-Z. Cai).
Corresponding author. Fax: ꢀ
/
86-791-851-7500.
1
compounds 5 has been proved by their H-NMR
0022-328X/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00583-7

M.-Z. Cai et al. / Journal of Organometallic Chemistry 681 (2003) 98Á
/
101
99
Scheme 1.
bromides. Investigations into the synthetic applications
of (Z,E)-2-phenylselenobutadienes (5) are currently in
progress.
Table 1
Synthesis of (Z,E)-2-phenylselenobutadienes 5aÁ5i
/
1
R in 4
a
Yield (%)
R in 1
Product 5
n-C
Ph
4
H
9
Ph
Ph
Ph
5a
5b
5c
5d
5e
5f
85
72
67
82
77
74
83
76
65
3
. Experimental details
CH
n-C
Ph
3
OCH
2
2
2
4
H
9
n-C
n-C
n-C
n-C
n-C
n-C
4
H
4
H
4
H
6
H
6
H
6
H
9
Cp Zr(H)Cl was prepared according to literature [16].
2
9
Solvent THF was distilled from sodiumÁbenzophenone
/
CH
n-C
Ph
3
OCH
9
1
ketyl before use. H-NMR spectra were recorded on a
Bruker AC-P200 (200 MHz) or Bruker AC-P500 (500
MHz) spectrometer with TMS as internal standard in
4
H
9
13
13
13
5g
5h
5i
3
CH OCH
CDCl . IR spectra were determined on an FTS-185
3
a
Isolated yield based on compound 4.
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.
spectra, which show a doublet at dꢁ
coupling constant of 15Á
/
6.0Á
/
6.8 ppm with a
/16 Hz, and this is also the
evidence of the retention of the E-configuration of the
starting compounds 3. In addition, the configuration of
the dienyl selenide 5b could be confirmed from com-
pound 6 which was obtained by treatment of 5b with n-
butyllithium in THF followed by hydrolysis, a reaction
which occurs stereoselectively (Scheme 2). The stereo-
chemistry of compound 6 was easily established, since
3
.1. General procedure for the synthesis of 5aÁ5i
/
A dry 25 ml round-bottomed flask was charged with 2
1.5 mmol). THF (8 ml) was injected, followed by
(
addition of 1 (1.5 mmol) at r.t. The mixture was stirred
at r.t. for 30 min under nitrogen to yield a clear solution.
It was then added with 4 (1.0 mmol) and Pd(PPh3)4
1
H-NMR spectrum (500 MHz) of 6 gives rise to a
doubletÁ
stants of 14.7 and 9.1 Hz and a doubletÁ
.68 ppm with coupling constants of 14.6 and 9.0 Hz,
which is consistent with an (E,E)-configuration. The
melting point of compound 6 was determined to be 147Á
48 8C which is also consistent with an (E,E)-config-
uration [15].
/
doublet at dꢁ
/
6.97 ppm with coupling con-
(1.0ꢂ5% mmol) and stirred at r.t. for 5 h. The mixture
/
/
doublet at dꢁ
/
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 flash chromatography on silica gel eluting with light
petroleum ether.
6
/
1
In conclusion, we have developed a novel route to the
synthesis of (Z,E)-2-phenylselenobutadienes via palla-
dium-catalyzed cross-coupling reaction. The major ad-
vantages of this coupling reaction are the preparation
convenience of (E)-a-phenylselenovinyl bromides (4) via
the addition of hydrogen bromide to alkynyl phenyl
selenides and the configuration retention of both the
starting alkenylzirconium complexes and the alkenyl
3.1.1. (1Z,3E)-1-Phenyl-2-phenylseleno-1,3-octadiene
(5a)
IR (film): n (cmꢃ1) 3056, 3021, 2955, 2926, 1634,
1
1597, 1491, 1476, 735, 690. H-NMR: d 7.13Á
/7.56 (m,
1
0
1
1H), 6.23 (m, 2H), 2.40 (m, 2H), 1.22Á
.90 (t, Jꢁ6.5 Hz, 3H) ppm. MS: m/z 341 ([M ], 12),
78 (100). Anal. Found: C, 70.22; H, 6.28. Calc. for
/
1.45 (m, 4H),
ꢀ
/
C H Se: C, 70.38; H, 6.45%.
0
2
22
3.1.2. (1Z,3E)-1,4-Diphenyl-2-phenylseleno-1,3-
butadiene (5b)
IR (film): n (cmꢃ1) 3057, 3024, 1596, 1576, 1493, 736,
1
6
90. H-NMR: d 7.02Á
/
7.62 (m, 18H) ppm. MS: m/z 362
ꢀ
([M ], 16), 77 (100). Anal. Found: C, 73.25; H, 4.84.
Calc. for C H Se: C, 73.13; H, 4.99%.
Scheme 2.
2
2
18

100
M.-Z. Cai et al. / Journal of Organometallic Chemistry 681 (2003) 98Á101
/
3
.1.3. (1Z,3E)-1-Phenyl-2-phenylseleno-5-methoxy-1,3-
pentadiene (5c)
IR (film): n (cm ) 3056, 3020, 2924, 1639, 1577,
3.1.9. (2E,4Z)-1-Methoxy-4-phenylseleno-2,4-
undecadiene (5i)
ꢃ1
ꢃ1
IR (film): n (cm ) 3058, 3039, 2924, 2854, 1645,
1
1
1
7
3
491, 1122, 735, 690. H-NMR: d 7.15Á
.09 (s, 1H), 6.45 (d, Jꢁ16.0 Hz, 1H), 6.32 (m, 1H),
.99 (d, Jꢁ6.0 Hz, 2H), 3.30 (s, 3H) ppm. MS: m/z 330
/
7.54 (m, 10H),
1578, 1476, 1438, 1123, 734, 689. H-NMR: d 7.13Á
/
7.33
7.0 Hz,
5.8 Hz, 2H), 3.23 (s, 3H),
1.42 (m, 8H), 0.87 (t, Jꢁ6.5 Hz,
3H). MS: m/z 338 ([M ], 14), 45 (100). Anal. Found: C,
/
(m, 5H), 6.32 (d, Jꢁ
1H), 6.13 (m, 1H), 3.94 (d, Jꢁ
2.45 (m, 2H), 1.25Á
/
15.2 Hz, 1H), 6.24 (t, Jꢁ
/
/
/
ꢀ
([M ], 17), 115 (100). Anal. Found: C, 65.47; H, 5.41.
Calc. for C H OSe: C, 65.65; H, 5.47%.
/
/
ꢀ
1
8
18
64.15; H, 7.81. Calc. for C H OSe: C, 64.09; H, 7.72%.
18 26
3
.1.4. (5Z,7E)-6-Phenylseleno-5,7-dodecadiene (5d)
ꢃ1
3
(
.2. Synthesis of (1E,3E)-1,4-diphenyl-1,3-butadiene
6)
IR (film): n (cm ) 3058, 3015, 2942, 1578, 1476,
1
1
438, 734, 689. H-NMR: d 7.15Á
/
7.54 (m, 5H), 6.53 (t,
2.45 (m, 4H), 1.18Á
1.08 (m, 6H) ppm. MS: m/z 322
[M ], 28), 81 (100). Anal. Found: C, 67.13; H, 8.04.
Calc. for C H Se: C, 67.29; H, 8.10%.
Jꢁ
1
(
/
7.0 Hz, 1H), 6.09 (m, 2H), 2.05Á
/
/
n-BuLi (1.6 M hexane solution, 1.1 mmol) was added
.52 (m, 8H), 0.69Á
/
ꢀ
to a THF (5.0 ml) solution of 5b (0.361 g, 1.0 mmol) at
78 8C. After stirring for 30 min, the mixture was
hydrolyzed with saturated aqueous NH Cl and ex-
ꢃ
/
1
8
26
4
tracted with CH Cl (2ꢂ10 ml). The organic extract
/
2
2
3
(
.1.5. (1E,3Z)-1-Phenyl-3-phenylseleno-1,3-octadiene
5e)
was dried (MgSO ) and the solvent was removed under
reduced pressure. The residue was purified by column
chromatography over silica gel using light petroleum
4
IR (film): n (cmꢃ1) 3058, 3024, 2956, 2870, 1623,
1
1
1
2
578, 1493, 1476, 734, 689. H-NMR: d 7.14Á
/
7.47 (m,
7.0 Hz, 1H),
1.49 (m, 4H), 0.90 (t, Jꢁ6.5 Hz, 3H)
ether as eluent to give 6 (0.166 g, 81%). m.p. 147Á
/
1H), 6.83 (d, Jꢁ
/
16.0 Hz, 1H), 6.37 (t, Jꢁ
/
1
(
48 8C, literature [15] m.p. 149Á150 8C. IR (KBr): n
/
.43 (m, 2H), 1.27Á
/
/
ꢃ1
1
cm ) 3054, 3015, 1635, 1593, 1490, 992, 739, 690. H-
ꢀ
ppm. MS: m/z 342 ([M ], 10), 129 (100). Anal. Found:
C, 70.51; H, 6.39. Calc. for C H Se: C, 70.38; H,
6
NMR (500 MHz, CDCl ): d 7.45 (d, Jꢁ
/7.5 Hz, 4H),
3
2
0
22
7
.22Á
/
7.35 (m, 6H), 6.97 (dd, Jꢁ/14.7, 9.1 Hz, 2H), 6.68
.45%.
(dd, Jꢁ/14.6, 9.0 Hz, 2H).
3
.1.6. (2E,4Z)-1-Methoxy-4-phenylseleno-2,4-
nonadiene (5f)
IR (film): n (cm ) 3057, 3038, 2924, 1644, 1578,
Acknowledgements
ꢃ1
1
1
5
6
476, 1438, 1123, 734, 689. H-NMR: d 7.14Á
H), 6.31 (d, Jꢁ15.2 Hz, 1H), 6.24 (t, Jꢁ7.0 Hz, 1H),
.13 (m, 1H), 3.94 (d, Jꢁ5.8 Hz, 2H), 3.30 (s, 3H), 2.42
1.42 (m, 4H), 0.88 (t, Jꢁ7.0 Hz, 3H)
/
7.39 (m,
We thank the National Natural Science Foundation
of China (Project No. 20062002) for financial support.
/
/
/
(
m, 2H), 1.26Á
/
/
ꢀ
ppm. MS: m/z 310 ([M ], 41), 45 (100). Anal. Found:
C, 62.30; H, 7.21. Calc. for C H OSe: C, 62.14; H,
References
1
6
22
7
.12%.
[
[
[
1] Y.Z. Huang, L. Shi, J. Yang, J. Zhang, Tetrahedron Lett. 28
1987) 2159.
2] E. Arce, M.C. Carreno, M.B. Cid, J.L.G. Ruano, J. Org. Chem.
9 (1994) 3421.
(
3
.1.7. (5E,7Z)-7-Phenylseleno-5,7-tetradecadiene (5g)
ꢃ1
5
IR (film): n (cm ) 3058, 3016, 2925, 2855, 1638,
3] (a) R. Ideses, A. Shani, Tetrahedron 45 (1989) 3523;
(b) J.B. Baudin, G. Hareau, S.A. Julia, R. Lorne, O. Ruel, Bull.
Soc. Chim. France 130 (1993) 856.
1
1
5
578, 1476, 1438, 733, 688. H-NMR: d 7.15Á
/
7.55 (m,
2.45
1.02 (m, 6H) ppm.
MS: m/z 349 ([M ], 13), 109 (100). Anal. Found: C,
H), 6.53 (t, Jꢁ
/
7.0 Hz, 1H), 6.08 (m, 2H), 2.06Á
1.58 (m, 12H), 0.72Á
/
[
4] (a) E. Negishi, T. Takahashi, S. Baba, D.E. Van Horn, N.
Okukado, J. Am. Chem. Soc. 109 (1987) 2393;
(
m, 4H), 1.18Á
/
/
ꢀ
(b) J.K. Stille, B.L. Groh, J. Am. Chem. Soc. 109 (1987) 813;
(c) K.S. Chan, C.C. Mak, Tetrahedron 50 (1994) 2003.
6
8.59; H, 8.51. Calc. for C H Se: C, 68.77; H, 8.60%.
20 30
[
[
5] T.H. Chan, J.S. Li, J. Chem. Soc. Chem. Commun. (1982)
6
96.
3
(
.1.8. (1E,3Z)-1-Phenyl-3-phenylseleno-1,3-decadiene
5h)
6] V. Fiandanese, G. Marchese, G. Mascolo, F. Naso, L. Ronzini,
Tetrahedron Lett. 29 (1988) 3705.
[7] F. Naso, Pure Appl. Chem. 60 (1988) 79.
IR (film): n (cmꢃ1) 3057, 3024, 1623, 1578, 1493,
1
[
8] (a) J.V. Comasseto, J. Organomet. Chem. 253 (1983) 131;
b) L. Hevesi, B. Hermans, C. Allard, Tetrahedron Lett. 35 (1994)
729.
9] L.S. Zhu, Z.Z. Huang, X. Huang, Tetrahedron 52 (1996)
819.
[10] J.V. Comasseto, C.A. Brandt, Synthesis (1987) 146.
1
476, 1437, 733, 689. H-NMR: d 7.14Á
/
7.54 (m, 11H),
7.0 Hz, 1H), 2.45
1.55 (m, 8H), 0.88 (t, Jꢁ6.5 Hz, 3H).
MS: m/z 370 ([M ], 10), 43 (100). Anal. Found: C,
1.37; H, 6.95. Calc. for C H Se: C, 71.54; H, 7.05%.
(
6
.81 (d, Jꢁ
/
16.0 Hz, 1H), 6.37 (t, Jꢁ
/
6
(
m, 2H), 1.14Á
/
/
[
ꢀ
9
7
2
2
26

M.-Z. Cai et al. / Journal of Organometallic Chemistry 681 (2003) 98Á
/
101
101
[
[
11] Y. Ma, X. Huang, J. Chem. Soc. Perkin Trans. 1 (1997) 2953.
12] E. Negishi, D.E. Van Horn, J. Am. Chem. Soc. 99 (1977)
[14] J.V. Comasseto, P.H. Menezes, H.A. Stefani, G. Zeni, A.L.
Braga, Tetrahedron 52 (1996) 9687.
3
168.
[15] G. Markl, A. Merz, Synthesis (1973) 295.
[16] J. Schwartz, J.A. Labinger, Angew. Chem. Int. Ed. Engl. 15
(1976) 333.
[
13] E. Negishi, H. Okukado, A.O. King, D.E. Van Horn, B.I.
Spiegol, J. Am. Chem. Soc. 100 (1978) 2254.