178 JOURNAL OF CHEMICAL RESEARCH 2007
(m, 8H), 1.05–0.69 (m, 6H); MS: m/z 322 (M+, 28), 81 (100), 77
(37), 57 (51); Anal. Calc. for C18H26Se: C, 67.27; H, 8.15. Found: C,
67.05; H, 7.9%.
in good yields. The experimental results are summarised in
Table 1. As shown in Table 1, the hydrostannylation-Stille
tandem reaction of Bu3SnH with a variety of acetylenic
selenides and alkenyl iodides proceeded smoothly under very
mild conditions to afford stereoselectively the corresponding
2-selenenyl-substituted 1,3-dienes 3.
Compound 3c: Oil. IR (film): ν (cm-1) 3057, 3038, 2924, 1644,
1
1578, 1476, 1438, 1123, 734, 689; H NMR (CDCl3): δ 7.39–7.14
(m, 5H), 6.31 (d, J = 15.2 Hz, 1H), 6.24 (t, J = 7.6 Hz, 1H), 6.18–6.09
(m, 1H), 3.94 (t, J = 5.8 Hz, 2H), 3.30 (s, 3H), 2.47–2.39 (m, 2H),
1.42–1.26 (m, 4H), 0.89 (t, J = 7.2 Hz, 3H); MS: m/z 310 (M+, 41),
77 (28), 57 (33), 45 (100); Anal. Calc. for C16H22OSe: C, 62.12; H,
7.17. Found: C, 61.9; H, 7.1%.
It is well documented that the Stille coupling reaction of
vinylstannanes with organic halides in the presence of a
palladium catalyst occurs with retention of configuration.17,18
The E-configuration of the R2 substituted double bond
compounds 3a, 3c, 3e, and 3h has been proved by their
1H NMR spectra which show a doublet at δ = 6.31–6.96
with a coupling constant of 15.2–16.4 Hz, and this is also
the evidence of the retention of the E-configuration of the
starting alkenyl iodides. In addition, the Z-configuration of the
n-Bu and SePh groups of the compound 3c was confirmed
Compound 3d: Oil. IR (film): ν (cm-1) 2980, 1583, 1457, 1114;
1H NMR (CDCl3): δ 6.37–6.33 (m, 1H), 5.65 (t, J = 5.8 Hz, 1H),
3.59 (d, J = 5.8 Hz, 2H), 3.39 (s, 3H), 2.08 (s, 3H), 2.20–2.01 (m,
4H), 1.61–1.46 (m, 4H); MS: m/z 246 (M+, 18), 151 (43), 106 (5), 45
(100); Anal. Calc. for C11H18OSe: C, 53.87; H, 7.40. Found: C, 53.6;
H, 7.1%.
Compound 3e: Oil. IR (film): ν (cm-1) 3052, 3024, 2996, 1578, 1477,
1118; 1H NMR (CDCl3): δ 7.47–7.04 (m, 6H), 6.78 (d, J = 16.4 Hz,
1H), 6.22 (t, J = 6.0 Hz, 1H), 4.37 (d, J = 6.0 Hz, 2H), 3.48 (s, 3H),
2.10 (s, 3H); MS: m/z 268 (M+, 11), 173 (53), 141 (100), 45 (27);
Anal. Calc. for C13H16OSe: C, 58.42; H, 6.03. Found: C, 58.55;
H, 6.15%.
1
by the NOESY in the H NMR spectrum. An enhancement
of the allylic protons of the n-Bu graph was observed as
the vinylic proton (δ = 6.24) of 3c was irradiated. There was
no correlation between the vinylic proton (δ = 6.24) and
any aromatic protons. The correlation between the vinylic
proton (δ = 6.24) and another vinylic proton (δ = 6.31)
was also observed. The NOE results indicate that 3c has
the expected Z-configuration of the Se-substituted double
bond and the cross-coupling reaction of (E)-α-stannylvinyl
selenides with alkenyl iodides occurs with the configuration
retention of both the starting compounds 2 and the alkenyl
iodides.
In summary, we have developed an efficient and
stereoselectiveone-potmethodforthesynthesisof2-selenenyl-
substituted 1,3-dienes. The present method has the advantages
of readily available starting materials, straightforward and
simple procedures, mild reaction conditions and good yields.
The procedure should find wide application to the synthesis
of a large array of naturally occurring substances having the
1,3-diene system.
Compound3f:Oil.IR(film):ν(cm-1)2981,1580,1494,1115;1HNMR
(CDCl3): δ 6.58–6.27 (m, 2H), 5.91 (t, J = 6.1 Hz, 1H), 3.77 (d,
J = 6.1 Hz, 2H), 3.26 (s, 3H), 2.36–2.27 (m, 2H), 2.08 (s, 3H), 1.50–
1.19 (m, 6H), 0.90 (t, J = 7.2 Hz, 3H); MS: m/z 261 (M+, 26), 167
(34), 57 (100), 45 (26); Anal. Calc. for C12H22OSe: C, 55.16; H, 8.49.
Found: C, 55.3; H, 8.5%.
Compound 3g: Oil. IR (film): ν (cm-1) 2928, 1601, 1466, 1120;
1H NMR (CDCl3): δ 6.07–6.01 (m, 2H), 5.92 (t, J = 5.8 Hz, 1H), 3.89
(m, 2H), 3.33 (s, 3H), 2.45–2.40 (m, 2H), 2.02 (s, 3H), 1.58–1.21 (m,
8H), 0.89 (t, J = 7.2 Hz, 3H); MS: m/z 276 (M+, 38), 245 (11), 149
(35), 110 (100), 45 (39); Anal. Calc. for C13H24OSe: C, 56.71; H,
8.79. Found: C, 56.5; H, 8.6%.
Compound 3h: Oil. IR (film): ν (cm-1) 3082, 3059, 1601, 1577,
1494, 1118; 1H NMR (CDCl3): δ 7.39–7.16 (m, 10H), 6.96–6.79
(dd, J = 16.0 Hz, 2H), 6.18 (t, J = 5.9 Hz, 1H), 4.24 (d, J = 5.9 Hz,
2H), 3.29 (s, 3H); MS: m/z 330 (M+, 12), 173 (50), 77 (100), 45
(70); Anal. Calc. for C18H18OSe: C, 65.65; H, 5.51. Found: C, 65.8;
H, 5.5%.
Compound 3i: Oil. IR (film): ν (cm-1) 3090, 3045, 1580, 1477,
1
1116; H NMR (CDCl3): δ 7.68–7.17 (m, 5H), 6.38–6.32 (m, 1H),
5.90 (t, J = 5.8 Hz, 1H), 4.16 (d, J = 5.8 Hz, 2H), 3.33 (s, 3H), 2.58–
2.40 (m, 4H), 1.67–1.15 (m, 4H); MS: m/z 308 (M+, 72), 151 (85),
121 (100), 77 (27), 45 (59); Anal. Calc. for C16H20OSe: C, 62.53; H,
6.56. Found: C, 62.3; H, 6.3%.
Experimental
1H NMR spectra were recorded on a Bruker AC-P300 (300 MHz)
spectrometer with TMS as an internal standard 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.
Benzene was distilled from sodium prior to use. DMF was dried by
distillation over calcium hydride.
We thank the National Natural Science Foundation of China
(Project No. 20462002) and the Natural Science Foundation
of Jiangxi Province of China (Project No. 0420015) for
financial support.
General procedure for the synthesis of 2-selenenyl-substituted 1,3-
dienes 3a–i
Received 22 February 2007; accepted 27 March 2007
Paper 07/4502
doi: 10.3184/030823407X200047
A 25 ml, two-necked, round-bottom flask equipped with a magnetic
stirring bar and under argon was charged sequentially with
the acetylenic selenide 1 (1 mmol), benzene (4 ml), Pd(PPh3)4
(0.05 mmol) and Bu3SnH (1.05 mmol). The mixture was stirred at
room temperature for 5 h. The solvent was removed under reduced
pressure and the residue was dissolved in DMF (10 ml). Then the
alkenyl iodide (0.9 mmol) and CuI (0.7 mmol) were added and the
mixture was stirred at room temperature for 8–10 h. The reaction
mixture was diluted with diethyl ether (30 ml), filtered and then treated
with 20% aqueous KF (10 ml) for 30 min before being dried and
concentrated. The residue was purified by column chromatography
on silica gel, eluting either a mixture of diethyl ether and petrol or
just petrol.
References
1
(a) K. Mori, in: J. ApSimon (ed.), The total synthesis of natural products:
the synthesis of insect pheromones, Vol. 4, Wiley, New York, 1981;
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28, 2159; (c) G.A. Molander and Y. Yokoyama, J. Org. Chem., 2006, 71,
2493.
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3
(a) R. Ideses and A. Shani, Tetrahedron, 1989, 45, 3523; (b) J.B. Baudin,
G. Hareau, S.A. Julia, R. Lorne and O. Ruel, Bull. Soc. Chim. France,
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(a) E. Negishi, T. Takahashi, S. Baba, D.E. Van Horn and N. Okukado,
J. Am. Chem. Soc., 1987, 109, 2393; (b) K.S. Chan and C.C. Mak,
Tetrahedron, 1994, 50, 2003.
Compound 3a: Oil. IR (film): ν (cm-1) 3058, 3024, 2956, 2870,
4
5
A. Kasatkin and R.J. Whitby, J. Am. Chem. Soc., 1999, 121, 7039.
(a) A. Padwa, B. Harrison, S.S. Murphree and P.E. Yeske, J. Org. Chem.,
1989, 54, 4232; (b) M. Yoshimatsu and J. Hasegawa, J. Chem. Soc.,
Perkin Trans. 1, 1997, 211.
1
1623, 1578, 1493, 1476, 734, 689; H NMR (CDCl3): δ 7.47–7.14
(m, 11H), 6.83 (d, J = 16.2 Hz, 1H), 6.37 (t, J = 7.2 Hz, 1H), 2.47–
2.40 (m, 2H), 1.49–1.27 (m, 4H), 0.90 (t, J = 7.2 Hz, 3H); MS: m/z
342 (M+, 10), 129 (100), 77 (43), 57 (37); Anal. Calc. for C20H22Se:
C, 70.36; H, 6.49. Found: C, 70.1; H, 6.5%.
6
(a) T.Y. Luh and K.T. Wong, Synthesis, 1993, 349; (b) E. Negishi and
F.T. Luo, J. Org. Chem., 1983, 48, 1560; (c) Z.J. Ni, P.F. Yang,
D.K.P. Ng, Y.L. Tzeng and T.Y. Luh, J. Am. Chem. Soc., 1990, 112, 9356;
(d) M. Cai, W. Hao, H. Zhao and C. Song, J. Organomet. Chem., 2003,
679, 14.
Compound 3b: Oil. IR (film): ν (cm-1) 3058, 3015, 2942, 1578,
1476, 1438, 734, 689; 1H NMR (CDCl3): δ 7.54–7.15 (m, 5H), 6.53
(t, J = 7.6 Hz, 1H), 6.13–6.04 (m, 2H), 2.45–2.05 (m, 4H), 1.52–1.18
PAPER: 06/4502