Mild and recyclable hypervalent iodine system for oxidation of alcohols

Article abstract of DOI:10.1080/00397910600978242

A simple and mild system for oxidation of primary and secondary alcohols to corresponding aldehydes and ketones has been developed using 4,4′-bis (dichloroiodo) biphenyl in combination with tetraethylammonium bromide (TEAB) at room temperature. Facile recovery and recyclability of the oxidant is reported. Copyright Taylor & Francis Group, LLC.

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Mild and Recyclable Hypervalent Iodine
System for Oxidation of Alcohols
Vikas N. Telvekar a & Omkar P. Herlekar a
a Department of Pharmaceutical Sciences and Technology , University
Institute of Chemical Technology , Matunga, Mumbai, India
Published online: 10 Mar 2007.
To cite this article: Vikas N. Telvekar & Omkar P. Herlekar (2007) Mild and Recyclable Hypervalent
Iodine System for Oxidation of Alcohols, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 37:5, 859-863, DOI: 10.1080/00397910600978242
To link to this article: http://dx.doi.org/10.1080/00397910600978242
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Synthetic Communicationsw, 37: 859–863, 2007
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910600978242
Mild and Recyclable Hypervalent Iodine
System for Oxidation of Alcohols
Vikas N. Telvekar and Omkar P. Herlekar
Department of Pharmaceutical Sciences and Technology, University
Institute of Chemical Technology, Matunga, Mumbai, India
Abstract: A simple and mild system for oxidation of primary and secondary alcohols
to corresponding aldehydes and ketones has been developed using 4,40-bis (dichlor-
oiodo) biphenyl in combination with tetraethylammonium bromide (TEAB) at room
temperature. Facile recovery and recyclability of the oxidant is reported.
Keywords: alcohols, 4,40-bis(dichloroiodo)biphenyl, oxidation, recycle, tetraethyl-
ammonium bromide
INTRODUCTION
Hypervalent iodine reagents and reagent systems found widespread appli-
cations in organic synthesis because of their selectivity and simplicity. Dess
Martin periodinane (DMP) and iodoxybenzoic acid (IBX) emerged as
reagents of choice for various synthetically useful oxidative transform-
ations.[1,2] Major concerns with these reagents are that they are potentially
explosive, they are hazardous to stock, and the generated iodine(III) species
is usually not recycled or utilized.[3–5] Therefore, facile and efficient use of
the readily available and relatively stable iodine(III) reagents in place of
iodine(V) reagents has been long desired. There are few examples of the
oxidation of alcohols using iodine(III) reagents.[6–8] Existing methods are
limited to organic solvents and usually involve activation by use of Ru
or Yb catalyst or 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO); also
Received May 15, 2006
Address correspondence to Vikas N. Telvekar, Department of Pharmaceutical
Sciences and Technology, University Institute of Chemical Technology, Matunga,
Mumbai 400019, India. E-mail: vikastelvekar@rediffmail.com
859

860
V. N. Telvekar and O. P. Herlekar
reactions of these reagents with the organic substrate lead to iodobenzene as
the by-product, which is difficult to recover and reuse because of its high vola-
tility and solubility in organic solvents.
RESULTS AND DISCUSSION
Our group has been working extensively on development of novel method-
ologies under mild reaction conditions using hypervalent iodine reagents.[9]
Thus, we report our results on oxidation of primary and secondary alcohols
using 4,40-bis(dichloroiodo)biphenyl in the presence of tetraethylammonium
bromide (TEAB) at room temperature.
For our initial study, benzyl alcohol was chosen as a substrate, and the
reaction with 4,40-bis(dichloroiodo)biphenyl in the presence of TEAB was
performed (Scheme 1).
A variety of primary and secondary alcohols of aromatics, aliphatics,
steroids, and carbohydrates were prepared as per the literature procedure
and subjected to the reaction, and the results are presented in Table 1. The
results clearly indicate that aromatic alcohols substituted with electron-
donating groups such as methyl and methoxy undergo very fast oxidation
(entries 2, 3, 8, 9); the reaction time is only 25 min and has good yields. On
the other hand, if the aromatic ring is substituted with electron-withdrawing
groups such as nitro and chloro, the reaction gives comparatively lower
yields at slower reaction rates (entries 5, 6, 10, 11).
GENERAL PROCEDURE
Benzyl alcohol (1.08 g, 10 mmol) was added to a stirred suspension of 4,40-
bis(dichloroiodo)biphenyl (3.1 g, 5.5 mmol) and TEAB (2.32 g, 11 mmol)
in dry chloroform (10 ml) at room temperature. The reaction was monitored
by thin-layer chromatography (TLC) (25 min; reaction mixture become
clear). Reaction mixture was washed with water (2 ꢀ 25), followed
Scheme 1.

Hypervalent Iodine System
861
Table 1. Oxidation of alcohol using TEAB and 4,40-bis(dichloroiodo)biphenyla
Time Yield
(min) (%)d
Entry
1
Alcoholb
Product
20
93
2
3
25
94
20
94
4
5
20
35
95
90
6
35
90
7
8
9
25
25
20
95
93
95
10
11
12
35
40
45
90
90
91
13
14
25
30
93
93
(continued)

862
V. N. Telvekar and O. P. Herlekar
Table 1. Continued
Time Yield
(min) (%)d
Entry
15
Alcoholb
Product
25
20
90
92
16
17
18
19
45
40
25
90
90
92
20
25
45
30
93
90
25
21c
22
23
24
25
25
30
45
30
25
35
aAll reactions were carried out at room temperature using 1.0 equiv of substrate, 0.55
equiv of 4,40-bis(dichloroiodo)biphenyl and 1.1 equiv of TEAB in dry dichloroform.
bStarting compounds were prepared by standard literature procedure and confirmed
by reported data.
c1.0 equiv of substrate, 1.2 equiv of 4,40-bis(dichloroiodo)biphenyl and 2.3 equiv of
TEAB used.
dIsolated yields after column chromatography and structure confirmed by IR and 1H
NMR.

Hypervalent Iodine System
863
successively with 10% sodium bicarbonate (2 ꢀ 15 ml), 10% aqueous sodium
bisulfite solution (2 ꢀ 15 ml), and finally with water (2 ꢀ 10 ml). The chloro-
form layer was separated, dried over sodium sulfate, and concentrated in
vacuum, and the resultant residue was treated with hexane (25 ml). The pre-
cipitation of 4,40-diiodobiphenyl was filtered and washed with hexane. The
filtrate was dried over sodium sulfate and concentrated. The residue
obtained was further purified by silica-gel column chromatography (10%
EtOAc–hexane) to afford benzyladehyde.
Regeneration of 4,40-bis(Dichloroiodo)Biphenyl
Isolated 4,40-diiodo biphenyl from the reaction mixture was recrystallized and
dissolved in chloroform, and excess of chlorine was bubbled through the
solution for 1 h at 10–158C under stirring. 4,40-bis(Dichloroiodo)biphenyl
precipitate was filtered, washed with cold chloroform, and dried [mp 1558C
(dec), lit.[10] mp 1568C (dec)].
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