Abstract
A new polymer-supported hypervalent iodine reagent, polystyrene-supported
iodosylbenzene sulfate (PS-IBS), can be conveniently prepared by
the reaction of polystyrene-supported (diacetoxyiodo)benzene (PS-DIB)
with sodium bisulfate monohydrate under solvent-free conditions.
This new recyclable reagent effects clean and efficient oxidation
of a wide range of alcohols and sulfides to the corresponding carbonyl
compounds or sulfoxides in high conversions under mild conditions.
The final products are conveniently separated from the polymeric
byproduct by simple filtration and isolated in good purity after
evaporation of solvent. Recycling of the resin is possible with
minimal loss of activity after several reoxidations.
Key words
polymers - iodine - oxidation - iodosylbenzene(III)
sulfate - recyclable reagent
References and Notes
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7 Structure 3 is
assigned for polystyrene-supported iodosyl-benzene sulfate based
on X-ray single crystal data for the monomeric analogue 1 , which has been prepared using a similar
solid-state procedure. We realize that the presence of the polystyrene
chain may have a significant effect on the actual structure of the
iodosylbenzene sulfate moiety. The ESI-MS study of compound 1 in aq solution indicates the presence
of hydroxy(phenyl)iodonium ion, [PhI(OH)]+ and hydrated
iodosylbenzene, PhI(OH)2 .4a,b It is possible
that similar polymer-bound iodine(III) moieties are present the structure
of resin 3 .
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9
Preparation of
PS-IBS (3)
2 )8 (1.430
g, 3.0 mmol) and NaHSO4 ˙H2 O (0.414
g, 3.0 mmol) were grinded intensively in a mortar at r.t. for 10 min.
The resulting mixture was left to stay at r.t. overnight, then washed
with H2 O (3 × 3 mL), acetone
(3 × 3 mL), and Et2 O (3 × 3
mL) subsequently, and then dried in vacuum to give a yellow powder
(1.45 g). Elemental analysis: S, 2.18% (loading of S: 0.68
mmol/g). IR (KBr): ν = 3406,
2923, 1628, 1481, 1406, 1118, 1004, 819, 766, 619 cm-¹ .
10
General Procedure
for Oxidations Using PS-IBS
6 (0.2 mmol) or alcohol 5 (0.2
mmol) in aq MeCN (2 mL of MeCN-H2 O, 5:1) was
added PS-IBS 3 (206 mg, 0.140 mmol) and
KBr (2.4 mg, 0.02 mmol) at r.t., and the mixture was magnetically
stirred until the sulfide or alcohol was consumed (monitored by
TLC). The mixture was filtered, and the resin was washed with EtOAc
(3 × 1 mL). The filtrate was washed with
sat. NaHCO3 (3 mL) [for alcohols, the filtrate
may be washed with 5% H2 SO4 (3 mL) before
this operation], then extracted with EtOAc (3 × 2 mL).
The combined organic solution was washed with brine (3 mL), water
(3 mL), and dried over Na2 SO4 . The solvent was
evaporated to yield respective products 7 -9 ; the products were identified by comparison
of their MS and NMR spectra with commercially available samples.
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