Oxidative cleavage of epoxides using aqueous sodium paraperiodate

Article abstract of DOI:10.1080/00397910802372574

A simple and mild method in water for direct conversion of epoxides to corresponding aldehydes has been developed using sodium paraperiodate (Na3H2IO6). High yields of corresponding aldehydes were obtained. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910802372574

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Oxidative Cleavage of Epoxides
Using Aqueous Sodium
Paraperiodate
Vikas N. Telvekar a , Dharmeshkumar J. Patel a &
Sanket J. Mishra a
a Department of Pharmaceutical Sciences and
Technology , University Institute of Chemical
Technology, University of Mumbai , Mumbai, India
Published online: 22 Dec 2008.
To cite this article: Vikas N. Telvekar , Dharmeshkumar J. Patel & Sanket J. Mishra
(2008) Oxidative Cleavage of Epoxides Using Aqueous Sodium Paraperiodate, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 39:2, 311-315, DOI: 10.1080/00397910802372574
To link to this article: http://dx.doi.org/10.1080/00397910802372574
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Synthetic Communications1, 39: 311–315, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910802372574
Oxidative Cleavage of Epoxides Using Aqueous
Sodium Paraperiodate
Vikas N. Telvekar, Dharmeshkumar J. Patel,
and Sanket J. Mishra
Department of Pharmaceutical Sciences and Technology, University
Institute of Chemical Technology, University of Mumbai, Mumbai, India
Abstract: A simple and mild method in water for direct conversion of epoxides
to corresponding aldehydes has been developed using sodium paraperiodate
(Na3H2IO6). High yields of corresponding aldehydes were obtained.
Keywords: Aldehydes, epoxides, sodium paraperiodate
INTRODUCTION
There are few methods in literature for conversion of epoxides to
aldehydes. One-pot methods available include the use of RuCl3 Á H2O
or OsO4 in combination with oxidants such as NaIO4, oxone, and
NaOCl.[1,2] A few cases in the literature have reported the reaction of
periodic acid or metaperiodic acid with epoxides, resulting in the corre-
sponding carbonyl compound.[3] Activated iodosylbenzene monomer
was used for the direct conversion of epoxides to aldehydes.[4,5]
Most of these methods are unsatisfactory, because of their long
reaction time, harsh reaction conditions, use of complex reagents, and
sometimes tedious workup, which means that there is still scope for alter-
native reagent systems for direct conversion of epoxides to aldehydes.
Received May 17, 2008.
Address correspondence to Vikas N. Telvekar, Department of Pharmaceutical
Sciences and Technology, University Institute of Chemical Technology, University
of Mumbai, Matunga, Mumbai, India. E-mail: vikastelvekar@rediffmail.com
311

312
V. N. Telvekar, D. J. Patel, and S. J. Mishra
Hypervalent iodine has emerged as reagent of choice for oxidation of
a broad range of functionalities, mostly because of its environmentally
friendly nature and high selectivity. Our group has been working exten-
sively on the development of novel methodologies under mild reaction
conditions using the various iodine reagents.[6,7] Sodium paraperiodate
is commercially available as white crystalline solid. Because of its insolu-
bility in almost all organic solvents and even in water, it has not been
exploited until now.
RESULTS AND DISCUSSION
While working on oxidation systems, we observed that this reagent can
be used for direct oxidative cleavage of the epoxides rings to aldehydes.
For our initial studies, styrene epoxide was reacted with sodium paraper-
iodate. A mixture of styrene epoxide (10 mmol), sodium paraperiodate
(12 mmol) in water, and catalytically two to three drops of conc. sulphu-
ric acid was stirred at room temperature. The starting material was con-
sumed within 20 min as indicated by Thin-Layer Chromatography (TLC)
analysis. After workup and purification by silica-gel column chromato-
graphy (hexane–EtOAc, 9:1), benzaldehyde was isolated in 89% yield
(Scheme 1).
It is interesting that the reaction does not take place in the absence of
sulphuric acid.
Encouraged by these results, a variety of aromatic and aliphatic
epoxides were subjected to the reaction conditions, and the results are
presented in Table 1. It is clearly indicated that aromatic epoxides were
converted into corresponding aldehydes in 20–25 min in the good yields
(Table 1, entries 1–6), but in the case of aliphatic aldehydes, slower reac-
tion rates were observed (Table 1, entries 7 and 8). In the presence of
bulkier groups, the reaction rates are still slower (Table 1, entries 9
and 10).
A wide range of functional groups were tolerated by this protocol,
and at these reaction conditions, methoxy, ether, and ester groups were
stable, and no deprotection was observed (Table 1, entries 4–6).
Scheme 1. Oxidative cleavage of styrene epoxide to benzaldehyde.

Oxidative Cleavage of Epoxides
313
a
Table 1. Synthesis of aldehydes from epoxides using aqueous Na3H2IO6
No.
1
Substrateb
Product
Time(min)
20
Yield(%)c
89
2
3
25
20
87
84
4
5
6
30
20
25
83
85
86
7
8
30
30
85
80
9
50
83
(Continued )

314
V. N. Telvekar, D. J. Patel, and S. J. Mishra
Table 1. Continued
No.
10
Substrateb
Product
Time(min)
120
Yield(%)c
82
aTypically, Na3H2IO6 (12 mmol) reacted with epoxide (10 mmol) in water
(25 mL) at room temperature.
bStarting compounds were prepared by standard literature procedures.
cIsolated yields after column chromatography and structure confirmed by
1
comparison of IR and H NMR with those of authentic materials.
In summary, a novel method has been developed for oxidation of
epoxides to aldehydes using sodium paraperiodate in water at room
temperature. The method developed is mild, easy to work up, has short
reaction time, and gave good to excellent yields of aldehydes for both
aliphatic as well as aromatic substrates.
GENERAL PROCEDURE
Preparation of Benzaldehyde
A few drops of conc. sulphuric acid (three to four drops required) were
added to a stirred suspension of sodium paraperiodate (1.2 equiv) in
water (25 mL). In this solution, epoxide (1.0 equiv) was added. The resul-
tant mixture was stirred at it until the starting material had been comple-
tely consumed monitored by thin-layer chromatography, (TLC). The
reaction mixture was extracted with CHCl3 (25 ml), and this organic layer
was washed successively with 10% aq. NaHCO3 (2 Â 15 mL), 10% aq.
sodium bisulfite solution (2 Â 15 mL), and H2O (2 Â 20 mL). The organic
layer was dried over Na2SO4 and concentrated in vacuo. The residue
obtained was purified by silica-gel column chromatography (10%
EtOAc–hexane) to afford pure aldehydes.
ACKNOWLEDGMENT
We gratefully acknowledge University Grants Commission (UGC),
India, for financial support a UGC major research project.

Oxidative Cleavage of Epoxides
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