A novel synthesis of allyl sulfides and allyl selenides via Sm-BiCl3 system in aqueous media

Article abstract of DOI:10.1039/a807256f

Allyl sulfides and allyl selenides are synthesized via the reaction of allyl bromide with disulfides and diselenides promoted by the Sm-BiCl₃ system in aqueous media in moderate to good yields.

Full text of DOI:10.1039/a807256f

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280 J. CHEM. RESEARCH (S), 1999
J. Chem. Research (S),
1999, 280^281y
A Novel Synthesis of Allyl Sulfides and Allyl
Selenides via Sm^BiCl3 System in Aqueous Mediay
Zhuangping Zhan,a Genliang Lub and Yongmin Zhang*b
a College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310014,
P. R. Chin a
b Department of Chemistry, Hangzhou University, Hangzhou, 310028, P.R. China
Allyl sulfides and allyl selenides are synthesized via the reaction of allyl bromide with disulfides and diselenides
promoted by the Sm^BiCl3 system in aqueous media in moderate to good yields.
There has been considerable interest in performing
organometallic reactions in aqueous media.1 The most fre-
quent reason changing organometallic reactions from strictly
anhydrous organic solvents to aqueous media is the ease
of reaction in obviating the need for in£ammable anhydrous
organic solvents and a troublesome inert atmosphere. For
some reactions, e.g. alkylations of carbonyl group in
carbohydrates, it is of great help that the substrates didn't
need to be altered to suit their reaction in organic solvents.2
The most commonly used metals are zinc, tin, indium
and bismuth or BiCl3 ^Al, BiCl3 ^Zn and BiCl3 ^Fe systems.3
However, the type of aqueous organometallic reactions
seems to have been somewhat limited. It has been used
mainly in Barbier-type reactions. We have become interested
in other types of aqueous organometallic reaction, and to
our knowledge no reaction mediated by bismuth has been
used to prepare sul¢des and selenides. As a part of our work
in aqueous organometallic reactions, we wish to report here
that allyl bromide can react with disul¢des and diselenides
promoted by Sm^BiCl3 to give allyl sul¢des and selenides.
The products and the reaction conditions are shown in the
Table 1. The best yields are obtained under a nitrogen
atmosphere. The reaction can be carried out in air, but
the yields are lower than those obtained under a nitrogen
atmosphere. We examined the e¡ects of several solvents
and found that comparatively high yields are obtained from
THF^H2O and DMF^H2O systems.
Cleavage of S S and Se Se bonds can be achieved by
three major routes:6 oxidative cleavage,7 nucleophile-assisted
cleavage8 and radical-assisted cleavage.9 Although the
reaction mechanism of the catalytic BiCl3-mediated cleavage
is not clear, a catalytic cycle can be presumed in which some
allylbismuth reagent
1
is prepared via the proposed
mechanism10 (Scheme 1).
RYYR
BiBr3–n
Br
Y = S, Se
n
1
BiCl3
Bi(0)
(RY)nBiBr3–n
+
RY
SmCl3
Sm(0)
SmBr3
BiBr3
+
Br
Sm(0)
RY
Scheme 1 Proposed mechanism of catalytic BiCl3 ^Sm(O)
mediated reaction
Sul¢des and selenides are useful synthetic reagents and
intermediates in organic synthesis.4;11 Many synthetic
methods that involve cleavage of the
S S bond in sul¢des
and Se Se bond in selenides have been reported. Most
of them have some limitations.6 For example, the necessity
to synthesize the organometallic, loss of half-unit of disul¢de
and diselenide, strong base catalysis, the need for anhydrous
BiCl3 Sm
!
CH2 ˆCH CH2 Br ‡ RYYR
CH2 ˆCH CH2YR
THF H2O
organic solvents, etc. In contrast, the cleavage of
S S
Table 1 Reaction conditions and yields
Entry
Y
R
Solvent
Product
Atmosphere
Yield(%)
State
Oil4
1
2
3
4
5
6
7
8
9
10
11
12
13
S
S
S
S
S
S
Se
Se
Se
Se
Se
Se
Se
Ph
Ph
Ph
THF^H2O(20/5)
THF^H2O(20/5)
DMF^H2O(20/5)
THF^H2O(20/5)
THF^H2O(20/5)
THF^H2O(20/5)
THF^H2O(20/5)
THF^H2O(20/5)
DMF^H2O(20/5)
THF^H2O(20/5)
THF^H2O(20/5)
THF^H2O(20/5)
DMF^H2O(20/5)
PhSCH2CH=CH2
PhSCH2CH=CH2
PhSCH2CH=CH2
N2
Air
N2
N2
N2
N2
N2
Air
N2
N2
N2
N2
N2
87
47
83
84
85
71
77
56
90
82
80
69
75
p-CH3C6H4
p-ClC6H4
PhCH2
Ph
Ph
Ph
p-CH3C6H4
p-ClC6H4
n-C4H9
n-C4H9
p-CH3C6H4SCH2CH ˆ CH2
p-ClC6H4SCH2CH ˆ CH2
PhCH2SCH2CH ˆ CH2
PhSeCH2CH ˆ CH2
Oil4
Oil4
Oil4
Oil5
PhSeCH2CH ˆ CH2
PhSeCH2CH ˆ CH2
p-CH3C6H4SeCH2CH ˆ CH2
p-ClC6H4SeCH2CH ˆ CH2
n-C4H9SeCH2CH ˆ CH2
n-C4H9SeCH2CH ˆ CH2
Oil5
Oil5
Oil5
* To receive any correspondence.
and Se Se bonds by the Sm^BiCl3 system circumvents
these problems. The present procedure provides a simple
and easy alternative method for the synthesis of sul¢des
and selenides in moderate to good yields.
y This is a Short Paper as de¢ned in the Instructions for Authors,
Section 5.0 [see J. Chem. Research (S), 1999, Issue 1]; there is
therefore no corresponding material in J. Chem. Research (M).
CDRI comunication No.: 5740.

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J. CHEM. RESEARCH (S), 1999 281
Experimental
References
Typical Procedure.öIn a 50 ml three-neck £ask ¢tted with a re£ux
condenser, are placed Sm powder (0.3 g), BiCl3 (1mmol), allylic bro-
mide (1.5 mmol) and disul¢des (0.5 mmol) or diselenides (0.5 mmol).
The mixture was stirred at 60 8C for 12 h. It was extracted with
Et2O. After drying ꢀNa2SO4†, the solvent was evaporated in vacuo
and the product was isolated by preparative TLC on silica gel using
light petroleum (bp 30^60 8C) as eluent. The products were charac-
terized by their 1H NMR and IR spectra.
1
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We thank the National Natural Science Foundation of
China and the Laboratory of Orgnometallic Chemistry,
Shanghai Institute of Organic Chemistry, Chinese Academy
of Sciences for ¢nancial support.
8
9
I. Das and S. Roy, J. Organomet. Chem., 1994, 467, 223.
Received, 17th September 1998; Accepted, 4th January 1999
Paper E/8/07256F
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