Carbon-carbon bond formation using bismuth in a water medium

Article abstract of DOI:10.1016/S0040-4039(03)01649-6

In the presence of bismuth and ammonium chloride, allyl halides were found to react with aldehydes in a water medium at room temperature to give the corresponding homoallylic alcohols.

Full text of DOI:10.1016/S0040-4039(03)01649-6

TETRAHEDRON
LETTERS
Pergamon
Tetrahedron Letters 44 (2003) 6963–6964
Carbonꢀcarbon bond formation using bismuth in a water medium
Hisakazu Miyamoto,* Naoki Daikawa and Koichi Tanaka
Department of Applied Chemistry, Faculty of Engineering, Ehime University, Matsuyama, Ehime 790-8577, Japan
Received 30 April 2003; revised 4 June 2003; accepted 27 June 2003
Abstract—In the presence of bismuth and ammonium chloride, allyl halides were found to react with aldehydes in a water medium
at room temperature to give the corresponding homoallylic alcohols.
©
2003 Elsevier Ltd. All rights reserved.
Among group VB elements, bismuth is excepted to be
useful for organic synthesis in view of its enhanced
metallic character. Wada et al. have reported metallic
bismuth-mediated allylation of aldehydes in DMF to
aqueous ammonium chloride for 0.75 h at room tem-
perature was reported to give 61% yield. Allylation of
2
1a with 2a using bismuth in a water medium gave good
yield in comparison to allylation of 1a with 2a using Zn
in a water medium. Allylation of 1a with 2a using
bismuth in the absence of a solvent gave low yield.
Allylation of 1a with 2a using bismuth in THF did not
occur and 1a was recovered.
1
give homoallylic alcohols. It has been reported that the
synthesis of homoallylic alcohols by the Luche
2
3
4
reaction using Zn in DMF or water at room temper-
ature proceeded efficiently. Recently, organic reactions
in aqueous media, particularly in water, have received
much attention because water is economical and envi-
The results of allylation of aromatic aldehydes (1a–o)
with allyl bromide (2a) using bismuth in a water
medium at room temperature are shown in Table 2.
Allylation of methyl substituted benzaldehydes (1b–d)
afforded good yields. Allylation of chloride substituted
benzaldehydes (1h–j) did not occur and gave only the
starting material. Allylation of p-methoxy substituted
benzaldehyde (1m) also did not occur, giving only the
starting material.
5
ronmentally benign. We report the allylation of alde-
hydes (1) with allyl halides (2) using bismuth in a water
medium at room temperature to afford the correspond-
ing homoallylic alcohols (3) in good yields.
The results of allylation of benzaldehyde (1a) with allyl
bromide (2a) using bismuth for 8 h at room tempera-
ture are shown in Table 1. Allylation of 1a with 2a
using bismuth in the presence of ammonium chloride in
6
a water medium gave 98% yield of 3aa. Allylation of
The results of allylation of aliphatic aldehydes (1p–t)
with allyl bromide (2a) using bismuth in a water
1a with 2a using Zn in the presence of saturated
Table 1. Allylation of benzaldehyde (1a) with allyl bromide (2a) using bismuth for 8 h at room temperature
Entry
Additive reagent
Yield (%)
In water
In the absence of solvent
In THF
1
2
3
NH Cl
ZnCl2
None
98
54
65
46
36
11
0
0
0
4
Keywords: bismuth; allylation; benzaldehyde; allyl bromide.
*
Corresponding author. Tel.: +81-89-927-8537; fax: +81-89-927-8537; e-mail: miyamoto@eng.ehime-u.ac.jp
0
040-4039/$ - see front matter © 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0040-4039(03)01649-6

6
964
H. Miyamoto et al. / Tetrahedron Letters 44 (2003) 6963–6964
Table 2. Allylation of aromatic aldehydes with allyl bro-
mide in water at room temperature
Table 4. Allylation of benzaldehyde with allyl halides
using bismuth at room temperature
1
Ar
Time (h)
Yield (%)
2
Time (h)
Yield (%)
98
a
b
c
d
e
f
g
h
i
C H
8
5
5
98
93
88
87
53
69
69
6
5
o-Me-C H
m-Me-C H
p-Me-C H
o-NO -C H
m-NO -C H
4
p-NO -C H
o-Cl-C H4
m-Cl-C H4
R
X
6
4
6
4
5
a
b
c
H
Ph
H
Br
Br
Cl
Cl
8
16
16
16
6
4
a
16
16
16
5
5
5
–
2
6
4
10
2
6
a
d
Ph
–
2
6
4
a
–
–
6
a
a
Recovery.
6
a
j
p-Cl-C H4
–
6
k
l
m
n
o
o-MeO-C H
16
16
40
16
16
80
52
–
47
40
6
4
halides (2a–d) using bismuth in a water medium at
room temperature are shown in Table 4. Allylation of
benzaldehyde (1a) with cinnamyl bromide (2b) using
bismuth did not occur. Although allylation of 1a with
m-MeO-C H
6
4
a
p-MeO-C H
6
4
1-Naphthyl
2-Naphthyl
1
allyl chloride (2c) in DMF did not occur, the allylation
a
of 1a with allyl chloride (2c) in a water medium gave
Recovery.
1
0% yield. The allylation of 1a with cinnamyl chloride
(
2d) did not occur.
Table 3. Allylation of aliphatic aldehydes with allyl bro-
mide using bismuth for 16 h at room temperature
In conclusion, allylation of aldehydes (1) with allyl
bromide (2a) using bismuth in a water medium at room
temperature afforded homoallylic alcohols (3) in good
yields.
References
1. (a) Wada, M.; Akiba, K-y. Tetrahedron Lett. 1985, 26,
4211; (b) Wada, M.; Ohki, H. Yuki Gosei Kagaku
Kyokaishi 1989, 47, 425.
2
3
. Petrier, C.; Luche, J.-L. J. Org. Chem. 1985, 50, 910.
. Shono, T.; Ishifune, M.; Kashimura, S. Chem. Lett. 1990,
4
49.
. Wilson, S. R.; Guazzaroni, M. E. J. Org. Chem. 1989, 54,
087.
. Otto, S.; Engberts, J. B. F. N.; Kwak, J. C. T. J. Am.
Chem. Soc. 1998, 120, 9517.
4
5
6
3
. Typical procedure: A mixture of benzaldehyde (1a, 0.50 g,
4.71 mmol), allyl bromide (2a, 1.71 g, 14.1 mmol), ammo-
nium chloride (0.25 g, 4.71 mmol), bismuth (2.5 g, 11.8
mmol), and water (20 mL) was stirred at room tempera-
ture for 8 h. The reaction product was filtered, extracted
with ethyl acetate, washed with water, dried with MgSO4,
evaporated to give 1-phenyl-3-buten-1-ol (3aa, 0.68 g, 4.61
medium at room temperature are shown in Table 3.
Allylation of aliphatic aldehydes (1p–t) with allyl bro-
mide (2a) using bismuth with stirring for 16 h at room
temperature gave moderate yield. Allylation of propyl
aldehyde (1p) with 2a using bismuth gave 82% yield.
1
mmol, 98% yield). The purity of 3 was determined by H
The results of allylation of benzaldehyde (1a) with allyl
NMR spectroscopy.