Indium-mediated reductive dehalogenation of α-halocarbonyl compounds in water

Article abstract of DOI:10.1039/b005278g

Reactions of various α-halocarbonyl compounds 1 with indium in the presence of a catalytic amount of sodium dodecyl sulfate in water were performed to afford the corresponding parent carbonyl compounds 2 in excellent yields. The Royal Society of Chemistry 2000.

Full text of DOI:10.1039/b005278g

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Indium-mediated reductive dehalogenation of ꢀ-halocarbonyl
compounds in water†
Leeyoung Park,a Gyochang Keum,a Soon Bang Kang,a Kwan Soo Kimb and
Youseung Kim*a
1
a Biochemicals Research Center, Korea Institute of Science and Technology,
Cheongryang P.O. Box 131, Seoul 130-650, Korea.
E-mail: yosekim@kistmail.kist.re.kr; Fax: ϩ82-2-958-5189
b Department of Chemistry, Yonsei University, Seoul 120-749, Korea
Received (in Cambridge, UK) 3rd July 2000, Accepted 27th October 2000
First published as an Advance Article on the web 30th November 2000
Reactions of various α-halocarbonyl compounds 1 with indium in the presence of a catalytic amount of sodium
dodecyl sulfate in water were performed to afford the corresponding parent carbonyl compounds 2 in excellent yields.
sodium dodecyl sulfate (SDS) in water from room temperature
to 80 ЊC for the time required to complete the reaction yielded
the corresponding carbonyl compounds 2 in excellent yields.
As shown in Table 1, this dehalogenation procedure is effective
not only with α-haloketones, esters and acids but also with
amide compounds. Even the hindered compound, 3-bromo-
bornan-2-one was efficiently dehalogenated at 60 ЊC for 3 h
in 96% yield (entry c). In the case of α-chlorocarbonyl
Introduction
Recently, organic reactions that can be carried out in aqueous
media have become one of the most challenging areas in
organic synthesis due to the environmental benefits and favor-
able effects of water on chemical transformations.1 Especially,
the reactions mediated by indium in aqueous media are of
current interest for their considerable applications in organic
synthesis.2,3
compounds, the reaction was rather slow compared with the
bromo compounds and a slightly higher temperature was
While the reductive dehalogenation reactions of α-
halocarbonyl compounds
1 using various reagents such
required. An aliphatic α-bromoacid compound was reduced
to the parent acid by addition of 1 drop of 2 M HCl (entry
h). Also dehalogenation of α-halonitrile compounds was
successfully achieved under these reaction conditions as shown
in Table 1 (entries m–o).
To our knowledge this is the first report on dehalogenation of
α-halonitrile compounds in H2O. Without SDS as a surfactant,
the reactions proceeded slowly and most of the starting
materials in some cases were recovered after prolonged
reaction. The use of such micellar systems12 as reaction media
gave rise to remarkable rate enhancement.
as active metals, low-valent metals, metal hydrides, or halide
salts in organic solvents have been studied extensively,4,5 only
a quite limited number of procedures have been reported to
be conducted in aqueous media. These known methods are
effective with limited carbonyl functional groups,6,7 using
sonication,8 or suffer from low yields9 of products.
Our continuous efforts10 to explore the utility of indium
metal for organic synthesis in mild conditions led us to find that
α-halocarbonyl compounds 1 can be effectively reduced to the
In conclusion, we have developed a versatile, effective
and convenient dehalogenation procedure for converting
various α-halocarbonyl compounds 1 to the parent carbonyl
compounds 2 in water in excellent yields. The present dehalo-
genation reaction offers
a simple and easily performed
alternative to other known methods. These micellar systems
may also be applied to other indium-mediated reactions in
water.
Scheme 1
parent carbonyl compounds 2 in a reaction mediated by indium
in the presence of sodium dodecyl sulfate (SDS) in water. This
is the first case in which indium-mediated reductive dehalo-
genation of α-halocarbonyls is carried out in micellar systems.11
We wish to report herein the versatile and efficient dehalo-
genation method of various α-halocarbonyl compounds 1
using indium in water.
Experimental
All starting materials were obtained commercially from Aldrich
1
or prepared by known methods.† H (300 MHz) and 13C (75
MHz) spectra were recorded in deuteriochloroform, unless
otherwise stated, on a Varian Gemini 300 NMR spectrometer
with tetramethylsilane as internal standard. Mass spectra were
recorded on either a VG70-VSEQ(VG ANALYTICAL, UK) or
a Hewlett Packard MSD 5972 series spectrometer coupled with
a Hewlett Packard 5890 series II gas chromatograph. Melting
points were recorded on a Thomas-Hoover capillary melting
point apparatus at atmospheric pressure and are uncorrected.
Identification of the products was made on the basis of IR, 1H
NMR and mass spectral evidence in comparison with authentic
samples.
Results and discussion
Treatment of the α-halocarbonyl compounds 1 with 130–170
M% of indium powder (~100 mesh) in the presence of 1 M% of
† Details of the synthesis and analytical data for α-halocarbonyl
compounds 1a, 1i, 1j and 1l–1o are available as supplementary data.
For direct electronic access see http://www.rsc.org/suppdata/p1/b0/
b005278g/
4462
J. Chem. Soc., Perkin Trans. 1, 2000, 4462–4463
This journal is © The Royal Society of Chemistry 2000
DOI: 10.1039/b005278g

View Article Online
Table
1
Reductive dehalogenation of various α-halocarbonyl
compounds with indium metal in H2O
and indium powder (86.1 mg, 150 M%) were added. The
solution was heated to 60 ЊC for 4 h, and water (2 cm3) was
added. The solution was extracted with chloroform (5 × 3 cm3),
and the solution was concentrated under reduced pressure
after drying over MgSO4. The oily residue was purified by
filtration over a short column of silica gel using n-hexane–ethyl
acetate (6:1) as eluant to give 57.3 mg (96%) of aceto-
phenone 2b as a colorless oil after evaporation of the solvent.
The product was identical in all respects with an authentic
sample.
0.01 M SDS
in H2O
In H2O
α-Halocarbonyl
compounds 1
Temp./ Time/ Yield Time/ Yield
Entry
ЊC
h
(%)d
h
(%)d
a
80
6
94e
3
>99
b
c
60a
60
5
94e
4e
4
3
96
Acknowledgements
This work was fully supported by the Korea Institute of
Science and Technology and the Ministry of Science and
Technology.
24
96e
d
50
7
NRf
6
88e
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General method for the reductive dehalogenation of
ꢀ-halocarbonyl compounds†
Acetophenone (2b). To a stirred 0.01 M aqueous solution (0.5
cm3) of SDS, α-bromoacetophenone 1b (99.5 mg, 0.5 mmol)
J. Chem. Soc., Perkin Trans. 1, 2000, 4462–4463
4463