Simple system for cleavage of alkene C-C bond using aqueous sodium paraperiodate

Article abstract of DOI:10.1080/00397910802638578

A simple and mild method for direct conversion of alkenes to corresponding aldehydes has been developed using sodium paraperiodate (Na3H2IO6) in water. The reagent was found to give excellent yields of corresponding aldehydes.

Full text of DOI:10.1080/00397910802638578

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Simple System for Cleavage of
Alkene C–C Bond Using Aqueous
Sodium Paraperiodate
a
a
Vikas N. Telvekar , Sanket J. Mishra
&
a
Dharmeshkumar J. Patel
a
Department of Pharmaceutical Sciences and
Technology, University Institute of Chemical
Technology, University of Mumbai, Mumbai, India
Published online: 12 May 2009.
To cite this article: Vikas N. Telvekar , Sanket J. Mishra & Dharmeshkumar J.
Patel (2009) Simple System for Cleavage of Alkene C–C Bond Using Aqueous
Sodium Paraperiodate, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 39:12, 2146-2150, DOI:
10.1080/00397910802638578
To link to this article: http://dx.doi.org/10.1080/00397910802638578
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Synthetic Communications , 39: 2146–2150, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910802638578
Simple System for Cleavage of Alkene C–C Bond
Using Aqueous Sodium Paraperiodate
Vikas N. Telvekar, Sanket J. Mishra, and Dharmeshkumar J. Patel
Department of Pharmaceutical Sciences and Technology, University
Institute of Chemical Technology, University of Mumbai, Mumbai, India
Abstract: A simple and mild method for direct conversion of alkenes to corre-
sponding aldehydes has been developed using sodium paraperiodate (Na H IO )
3 2 6
in water. The reagent was found to give excellent yields of corresponding
aldehydes.
Keywords: Aldehyde, C–C double bond, sodium paraperiodate, water
INTRODUCTION
There are few methods in the literature for cleavage of alkene carbon–
carbon bond to aldehyde. Various one-pot methods are available, includ-
ing RuCl Á H O, OsO , clay in combination with oxidants such as NaIO ,
3
2
1–3]
4
4
[
and oxone.
Heterogeneous catalysts such as calcined heteropolyacids
on an oxide support in the presence of H O have also been reported for
2
2
[
cleavage. A few cases in the literature report carbon–carbon double
4]
bond oxidation by O over TiO =SiO and selective oxidation of styrenes
2
2
2
under O catalyzed by cobalt chloride as well as tert-butyl hydroperoxide
2
[5–7]
used in combination with AuCl.
Most of these methods are unsatisfactory because of their long
reaction times, harsh reaction conditions, use of complex reagents, and
Received October 16, 2008.
Address correspondence to Vikas N. Telvekar, Department of Pharmaceutical
Sciences and Technology, University Institute of Chemical Technology, Univer-
sity of Mumbai, Matunga, Mumbai 400019, India. E-mail: vikastelvekar@
rediffmail.com
2
146

Cleavage of Alkene C–C Bond
2147
sometimes tedious workup, which means that there is still scope for
alternative reagent systems for cleavage of alkene carbon–carbon bond
to aldehyde.
Hypervalent iodine has emerged as a reagent of choice for oxidation
of a broad range of functionalities, mostly because of their environmen-
tally friendly nature and high selectivity. Our group has been working
extensively on the development of novel methodologies under mild
[
8,9]
reaction conditions using the various iodine reagents.
Sodium para-
periodate is commercially available as a white crystalline solid. Because
of its insolubility in almost all organic solvents and even 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 cleavage of the alkene carbon–carbon bond to alde-
hydes. For our initial studies, styrene was reacted with sodium paraper-
iodate. A mixture of styrene (10 mmol), sodium paraperiodate (12 mmol)
ꢀ
in water, and a few drops of conc. sulfuric acid was stirred at 70 C. The
starting material was consumed within 3 h as indicated by thin-layer
chromatography (TLC). After workup and purification by silica-gel col-
umn chromatography (hexane–EtOAc, 9:1), benzaldehyde was isolated in
8
2% yield (Scheme 1).
The reaction does not take place in the absence of sulfuric acid.
Sodium paraperiodate is practically insoluble in water, but with a few
drops of sulfuric acid it forms a clear solution.
Encouraged by these results, a variety of aromatic and aliphatic
alkene compounds were subjected to the reaction conditions, and the
results are presented in Table 1. It is clearly indicated that the aromatic
alkene C–C bond was converted into corresponding aldehydes in 3–4 h
with good yields (Table 1, entries 1–8), but in the case of aliphatic
alkenes, the reaction does not take place even after a long time
(
Table 1, entries 9 and 10).
Scheme 1. Styrene to benzaldehyde using sodium paraperiodate.

2148
V. N. Telvekar, S. J. Mishra, and D. J. Patel
a
3 2 6
Table 1. Cleavage of carbon–carbon double bond using aqueous Na H IO
b
c
No.
1
Substrate
Product
Time (h)
3.0
Yield (%)
82
2
3.5
84
3
4
3.5
4.0
87
83
5
6
4.0
4.0
87
86
7
8
3.5
4.5
83
85
d
9
NR
24
24
—
—
1
0
NR
a
Typically, Na H IO (12 mmol) reacted with substrate (10 mmol) in water
2
3
6
ꢀ
(
25 mL) at 70 C.
b
Starting compounds were prepared by standard literature procedures.
Isolated yields after column chromatography and structure was confirmed by
c
1
comparison of IR and H NMR with those of authentic materials.
d
NR: no reaction.
A wide range of functional groups was tolerated by this protocol,
and in these reaction conditions methoxy, ether, and ester groups were
stable. No deprotection was observed (Table 1, entries 4–6).

Cleavage of Alkene C–C Bond
2149
In summary, a novel method has been developed for cleavage of the
alkene C–C bond to corresponding aldehydes using sodium paraperio-
ꢀ
date in water at 70 C. The method developed is mild, easy to workup,
and gives good to excellent yields of aldehydes for aromatic substrates.
GENERAL PROCEDURE
Preparation of Benzaldehyde
A few drops of conc. sulfuric acid were added to a stirred suspension of
sodium paraperiodate (12 mmol) in water (25 mL) until the solution
became clear (five to seven drops required). In this solution, styrene
ꢀ
(
10 mmol) was added. The resultant mixture was stirred at 70 C until
the starting material had been completely consumed (TLC). After the
completion of the reaction, the reaction mixture was extracted with
CHCl (25 ml). This organic layer was washed successively with 10%
3
aq. NaHCO (2 Â 15 mL), 10% aq. sodium bisulfite solution (2 Â 15 mL),
3
and H O (2 Â 20 mL), dried over Na SO , filtered, and concentrated in
2
2
4
vacuo. The residue obtained was purified by silica-gel column chromato-
graphy (10% EtOAc–hexane) to afford pure aldehyde.
ACKNOWLEDGMENT
We gratefully acknowledge the University Grants Commission, India, for
financial support under the scheme of a UGC major research project.
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