Bismuth Tribromide Catalyzed Oxidation of Alcohols with Aqueous Hydrogen Peroxide

Article abstract of DOI:10.1055/s-0035-1560467

An efficient bismuth tribromide catalyzed oxidation of various alcohols with aqueous hydrogen peroxide is described, leading to the corresponding carbonyl compounds.

Full text of DOI:10.1055/s-0035-1560467

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© Georg Thieme Verlag Stuttgart · New York
2015, 26, 2434–2436
letter
2434
M.-k. Han et al.
Letter
Synlett
Bismuth Tribromide Catalyzed Oxidation of Alcohols with Aque-
ous Hydrogen Peroxide
Mi-kyung Han
Sohwa Kim
O
OH
30% H2O2, BiBr3
R1
R2
R1
R2
70 °C, 10–40 min
70–96%
Sung Tae Kim
Jong Chan Lee*
23 examples
Department of Chemistry, Chung-Ang University,
Seoul 156-756, Republic of Korea
jclee@cau.ac.kr
Received: 14.07.2015
Accepted after revision: 07.08.2015
Published online: 02.09.2015
oxidative protocol for alcohols with more environmentally
benign and cost-effective reaction conditions is still a chal-
lenge.
DOI: 10.1055/s-0035-1560467; Art ID: st-2015-u0545-l
Water has received much attention as a greener alterna-
tive reaction medium to toxic and volatile organic solvents
for a variety of organic reactions.18 Water can exhibit
unique solvent behavior like rate acceleration19 and en-
hanced selectivity20 compared to reactions in conventional
organic solvents. However, the oxidation of primary alco-
hols with aqueous hydrogen peroxide often provided main-
ly over-oxidized carboxylic acid derivatives. For instance,
the oxidation of benzaldehyde in the presence of H2O2 and
Au/TiO2 provided benzoic acid.21 To date, only a few exam-
ples of methods for effective hydrogen peroxide mediated
oxidation of alcohols to the corresponding carbonyl com-
pounds in organic solvent-free aqueous systems have been
reported.22,23
Bismuth tribromide, an inexpensive, less toxic, and
readily available reagent, has been used in various organic
transformations such as halogen-exchange reactions,24 cya-
nation of carbonyl compounds,25 oxidation of sulfides to
sulfoxides,26 and preparation of alkyl ethers.27 However,
there is only a single example of the application of bis-
muth(III) complexes for the oxidation of alcohols. This
method utilized bismuth(III) nitrate in combination with
acidic zeolite materials in PEG 1500 for the oxidation of
benzylic alcohols to aldehydes.28
Abstract An efficient bismuth tribromide catalyzed oxidation of vari-
ous alcohols with aqueous hydrogen peroxide is described, leading to
the corresponding carbonyl compounds.
Key words alcohols, catalysis, green chemistry, oxidation, hydrogen
peroxide
The oxidative transformation of alcohols into the corre-
sponding carbonyl compounds occupies an important place
in the realm of synthetic organic chemistry.1,2 Numerous
methods have been developed for this conversion, and
some of the conventionally used protocols involve oxidants
like pyridinium chlorochromate,3 triphenylmethylphospho-
nium dichromate,4 oxone,5 iodine,6 Mn(OAc)3/DDQ,7 N-hy-
droxyindole/copper(I) chloride,8 and ruthenium hydrotal-
cite.9 Among others, hydrogen peroxide has attracted great
attention for the oxidation of alcohols due to its eco-friend-
ly nature and ready availability. In general, hydrogen perox-
ide has been utilized for the oxidation of alcohols in combi-
nation with sophisticated complexes of transition metals
such as aluminum,10 iron,11 manganese,12 molybdenum,13
or tungsten.14,15 In addition, hydrogen peroxide mediated
oxidations of alcohols with HBr16 or NaBr/AcOH17 have been
reported. However, many of them are associated with the
use of exotic transition-metal complexes, long reaction
times, modest isolated yields, and user-unfriendly, harsh
reaction conditions which limit their practical synthetic ap-
plication. Furthermore, the above-mentioned hydrogen
peroxide mediated oxidation methods generally use phase-
transfer catalysts in harmful volatile organic solvents which
are not desirable in a healthy environment.11 Therefore, de-
velopment of an alternative hydrogen peroxide mediated
To the best of our knowledge, the application of bismuth
tribromide for the oxidation of alcohols has not been previ-
ously reported. Thus, it is highly desirable to develop a new
environmentally benign method for the oxidation of alco-
hols to the corresponding carbonyl compounds utilizing
bismuth tribromide in combination with aqueous hydrogen
peroxide as an economical and greener oxidative system.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, 2434–2436

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M.-k. Han et al.
Letter
Synlett
As a part of our continued efforts to develop eco-friend-
ly oxidative procedures for alcohols, we report here a novel
method for the efficient oxidation of benzylic and aliphatic
alcohols by inexpensive and easily accessible bismuth
tribromide and aqueous 30% hydrogen peroxide. Treatment
of benzylic alcohols with 5.0 molar equivalents of hydrogen
peroxide and bismuth tribromide (10 mol%) for 10–40 min-
utes at 70 °C provided the corresponding oxidized carbonyl
compounds (Scheme 1). Initial attempts to oxidize primary
benzylic alcohols in the absence of bismuth did not provide
the desired benzaldehydes. Furthermore, to our surprise,
replacement of bismuth tribromide by bismuth trichloride
generally gave unchanged starting materials. The present
reaction protocol can be applied for the oxidation of a vari-
ety of primary and secondary alcohols and the results are
summarized in Table 1. Both primary and secondary ben-
zylic alcohols were efficiently oxidized to their correspond-
ing carbonyl compounds in high yields. In all cases of oxida-
tion of primary benzylicalcohols, our conditions resulted in
exclusive formation of aldehydes, without over-oxidized
carboxylic acids being detected. However, over-oxidized
carboxylic acid began to form in prolonged reaction times
of more than two hours. Moreover, electrophilic bromina-
tion at the aromatic ring was not observed in all the cases
tested. The position of substituents on the aromatic ring did
not influence the yields of the oxidation reactions (entries
2–5). In addition, the results demonstrated that electron-
donating or -withdrawing substituents on the aromatic
ring of the substrates did not significantly affect the effi-
ciency of the oxidation reactions. In general, the oxidation
of secondary benzylic alcohols proceeded faster than that of
primary alcohols. The protocol was also successfully appli-
cable to the oxidation of an allylic alcohol (entry 20) or ali-
phatic alcohols (entries 21–23) to provide the desired prod-
ucts in high yields. The oxidation presumably occurred by
the reaction of the alcohol with hypobromous acid, formed
in situ by the reaction of bismuth tribromide and hydrogen
peroxide, to give a hypobromite intermediate in line with a
previously reported analogous observation of the oxidation
of alcohols with NaBr–NaBrO3.29
Table 1 Oxidation of Alcohols with Hydrogen Peroxide and Bismuth
Tribromide
Entry Substrate
Product
Time
Yield
(min) (%)a
1
2
PhCH2OH
PhCHO
30
30
30
30
30
30
30
30
10
10
10
20
10
10
10
10
10
40
10
10
10
30
10
90
93
92
85
89
85
72
80
75
80
85
90
95
95
96
80
85
85
88
75
85
72
70
2-MeC6H4CH2OH
4-MeC6H4CH2OH
2-ClC6H4CH2OH
4-ClC6H4CH2OH
4-BrC6H4CH2OH
4-MeOC6H4CH2OH
4-O2NC6H4CH2OH
naphthalen-1-ylmethanol
PhCH(OH)Me
2-MeC6H4CHO
4-MeC6H4CHO
2-ClC6H4CHO
4-ClC6H4CHO
4-BrC6H4CHO
4-MeOC6H4CHO
4-O2NC6H4CHO
1-naphthaldehyde
PhCOMe
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
PhCH(OH)Et
PhCOEt
4-MeC6H4CH(OH)Me
4-ClC6H4CH(OH)Me
4-BrC6H4CH(OH)Me
4-FC6H4CH(OH)Me
1-(naphthalen-2-yl)ethanol
α-tetralol
4-MeC6H4COMe
4-ClC6H4COMe
4-BrC6H4COMe
4-FC6H4COMe
2-acetonaphthone
α-tetralone
PhCH(OH)Ph
PhCOPh
PhCH(OH)CO2Et
PhCH=CHCH2OH
cyclohexanol
PhCOCO2Et
PhCH=CHCHO
cyclohexanone
nonanal
1-nonanol
2-octanol
2-octanone
a Isolated yield.
Acknowledgment
This research was supported by the Chung-Ang University Graduate
Research Scholarship in 2015.
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© Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, 2434–2436

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Synlett
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(30) General Experimental Procedure for the Oxidation of Alco-
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oxide (5.0 mmol, 30% aq) was added BiBr3 (10 mol%). The reac-
tion mixture was stirred at 70 °C for 10–40 min, and the
reaction mixture was extracted with dichloromethane (2 × 5
mL). The combined organic layers were washed with saturated
brine (2 × 5 mL) and dried with anhydrous MgSO4. After evapo-
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chromatography (SiO2; CH2Cl2–hexane, 3:2) to afford the pure
carbonyl compound.
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Benzophenone (Table 1, entry 18): off-white solid; 155 mg
(85% yield). 1H NMR (300 MHz, CDCl3): δ = 7.68 (m, 4 H), 7.51–
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© Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, 2434–2436