Intramolecular oxyselenenylation and deselenenylation reactions in water, conducted by employing polymer-supported arylselenenyl bromide

Article abstract of DOI:10.1016/S0040-4039(03)00779-2

After immobilizing arylselenenyl bromide on polymer resin, the oxyselenenylation reaction of olefin was carried out in water. An amphiphilic polymer-supported arylselenenyl bromide was employed, and various intramolecular oxyselenenylation and deselenenylation reactions proceeded smoothly in water in fair chemical yields (up to an 83% yield).

Full text of DOI:10.1016/S0040-4039(03)00779-2

TETRAHEDRON
LETTERS
Pergamon
Tetrahedron Letters 44 (2003) 3793–3795
Intramolecular oxyselenenylation and deselenenylation reactions
in water, conducted by employing polymer-supported
arylselenenyl bromide
Ken-ichi Fujita,* Shigeru Hashimoto, Akihiro Oishi and Yoichi Taguchi
National Institute of Advanced Industrial Science and Technology (AIST), AIST Tsukuba Central 5, 1-1-1, Higashi, Tsukuba,
Ibaraki 305-8565, Japan
Received 3 March 2003; revised 13 March 2003; accepted 14 March 2003
Abstract—After immobilizing arylselenenyl bromide on polymer resin, the oxyselenenylation reaction of olefin was carried out in
water. An amphiphilic polymer-supported arylselenenyl bromide was employed, and various intramolecular oxyselenenylation and
deselenenylation reactions proceeded smoothly in water in fair chemical yields (up to an 83% yield). © 2003 Elsevier Science Ltd.
All rights reserved.
The use of organoselenium reagents in an organic syn-
thesis is now commonly accepted as a powerful tool for
introducing new functional groups into organic sub-
strates.1 Recently, several polymer-supported selenore-
agents were prepared, and their applications to
solid-phase organic synthesis and the combinatorial
approach were then reported by us2 and by other
groups.3
according to Scheme 1. In this scheme, the selenolac-
tonization reaction did not proceed smoothly in water,
so that the yield of the corresponding selenolactone 1
(49% yield) was decreased significantly as compared
with the yield obtained in dichloromethane (100%
yield). In the case of carrying out in water, we also
obtained diphenyl diselenide (36% yield), which was
produced by the decomposition of phenylselenenyl bro-
mide in water.5b On the other hand, the subsequent
oxidative deselenenylation reaction proceeded smoothly
in water to provide 2 in 77% yield, which was compara-
ble to the yield obtained in dichloromethane (90%
yield).
Owing to today’s environmental concerns about harm-
ful and volatile organic solvents, the use of organic
transformations in water is presently undergoing a very
rapid growth.4 However in selenium chemistry, most
organoselenium reagents are insoluble or decomposed
in water. For example, phenylselenenyl bromide, which
is a representative electrophilic selenoreagent, is easily
decomposed in water,5 but only a few transformations
employing selenoreagents in aqueous organic solvent
have been reported.6 We wish to report here the first
example of the oxyselenenylation and the subsequent
deselenenylation reactions in water, conducted by
employing polymer-supported arylselenenyl bromide.
We then carried out this two-step transformation in
water by employing polymer-supported arylselenenyl
bromide as follows (Scheme 2). We stirred 3a, which
was prepared from aminomethyl-polystyrene resin2a
(182 mg, 0.24 mmol) and (E)-styrylacetic acid (136 mg,
0.84 mmol) in water (3 ml) at room temperature for 15
h, and the corresponding polymer-supported selenolac-
tone 4a was then obtained. Subsequently, through the
We first employed phenylselenenyl bromide, which was
not immobilized, in order to examine the intramolecu-
lar oxyselenenylation (namely, selenolactonization) and
the subsequent deselenenylation reactions in water
Keywords: polymer-supported; selenium; solid-phase; oxyselenenyla-
tion; water.
* Corresponding author. Fax: +81-29-861-4511; e-mail: k.fujita@
aist.go.jp
Scheme 1.
0040-4039/03/$ - see front matter © 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0040-4039(03)00779-2

3794
K. Fujita et al. / Tetrahedron Letters 44 (2003) 3793–3795
Scheme 2.
Table 1. Selenolactonization and deselenenylation reactions of (E)-styrylacetic acid
oxidation of 4a, which was collected by filtration, with
30% hydrogen peroxide (0.11 ml, 1.0 mmol) in water (3
ml) at room temperature for 15 h followed by the usual
workup and by purification, the deselenenylation
product 2 (23 mg, 0.14 mmol) was obtained in a 59%
yield (Table 1, entry 2), which was higher than the yield
obtained by using phenylselenenyl bromide (entry 1).
This is probably because the decomposition of the
bromoselenenyl group in water is suppressed by immo-
bilizing the selenogroup on the polymer-backbone due
to its hydrophobicity. Especially in this case, the yield
of 2 obtained in water exceeded the yield obtained in
dichloromethane using 3a (46% yield). Although we
have no definitive explanation at the moment for high
yield obtained in water, the hydrophobic cohesion of
organic substrates in water could be responsible. This is
the first example of oxyselenenylation and deselenenyla-
tion reactions performed in water. In this method, it
should be noted that the selenocompound could be
easily recovered entirely by filtration after the desele-
nenylation process.
Scheme 3.
Table 2. Various intramolecular oxyselenenylation and
deselenenylation reactions in water using 3b
Encouraged by these results, we then proceeded to use
amphiphilic polymer-supported 3b, which was prepared
from poly(ethylene glycol)-polystyrene graft co-polymer
resin (ArgoGel®-NH2), similar to the preparation of
3a.2a In this case, the corresponding selenolactonization
and deselenenylation reaction proceeded more
smoothly in water with rapid resin decolorization than
those using 3a, due to its amphiphilic property (62%
yield; entry 3).
nenylation reactions, proceeded smoothly in water to
afford the corresponding deselenenylation products 5 in
fair total yields (up to an 83% yield; entry 5). This
method of realizing reactions in aqueous media by
immobilizing reagents, which are decomposed in water,
By employing 3b, we subsequently performed various
intramolecular oxyselenenylation and deselenenylation
reactions in water (Scheme 3, Table 2). Not only the
selenolactonization and deselenenylation reactions, but
also the intramolecular selenoetherification and desele-

K. Fujita et al. / Tetrahedron Letters 44 (2003) 3793–3795
3795
may be an effective approach to expanding the range of
organic syntheses carried out in water.
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We are currently trying to apply this method to other
reactions, and to the catalytic version. The results will
be reported in due course.
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