Regio-and stereoselective hydroxybromination and dibromination of olefins using ammonium bromide and oxone

Article abstract of DOI:10.1016/j.tetlet.2012.01.026

An efficient protocol for the synthesis of vicinal bromohydrins and dibromides from olefins is presented. Various olefins are regio-and stereoselectively hydroxybrominated and dibrominated with anti fashion, following Markonikov's rule, using eco-friendly, non-toxic, and stable reagents such as NH₄Br and oxone in CH₃CN/H₂O (1:1) and CH₃CN without employing catalyst in moderate to excellent yields. Bromohydrins are formed instantaneously.

Full text of DOI:10.1016/j.tetlet.2012.01.026

Tetrahedron Letters 53 (2012) 1401–1405
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Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
Regio- and stereoselective hydroxybromination and dibromination
of olefins using ammonium bromide and oxoneÒ
⇑
Arun Kumar Macharla, Rohitha Chozhiyath Nappunni, Narender Nama
I&PC Division, Indian Institute of Chemical Technology, Hyderabad 500 007, India
a r t i c l e i n f o
a b s t r a c t
Article history:
An efficient protocol for the synthesis of vicinal bromohydrins and dibromides from olefins is presented.
Various olefins are regio- and stereoselectively hydroxybrominated and dibrominated with anti fashion,
following Markonikov’s rule, using eco-friendly, non-toxic, and stable reagents such as NH4Br and oxoneÒ
in CH3CN/H2O (1:1) and CH3CN without employing catalyst in moderate to excellent yields. Bromohy-
drins are formed instantaneously.
Received 18 October 2011
Revised 4 January 2012
Accepted 6 January 2012
Available online 12 January 2012
Ó 2012 Elsevier Ltd. All rights reserved.
Keywords:
Alkenes
Hydroxybromination
Dibromination
Regioselectivity
Stereoselectivity
Regioselective functionalization of olefins is an important pro-
cess in synthetic organic chemistry. In particular, selective intro-
duction of two functional groups, such as hydroxybromo and
dibromo in a highly regio- and stereoselective manner remains
an important and challenging task.1 The resulting products (vicinal
bromohydrins and dibromides) are versatile intermediates for the
synthesis of pharmaceuticals, dyes, flame retardants, agrochemi-
cals, additives, plasticizers, and specialty chemicals.2
Bromohydrins are usually prepared by the ring opening of epox-
ides3 using hydrogen bromide or metal bromides. These proce-
dures are generally associated with the formation of byproducts
such as vicinal dibromides, 1,2-diols and these methods also re-
quire prior synthesis of epoxides. Apart from this, there are two
general approaches for heterolytic addition of water and bromine
to an olefinic bond. One, involves the use of molecular bromine
or N-bromoimides4,7 and the other uses metal bromide or HBr
along with an oxidizing agent.5,6
number of protocols are available to achieve bromination of
alkenes using BrÀ instead of Br2. The oxidative bromination requires
a metal salt as bromine source, an oxidizing agent and a catalyst to
carry out the transformation. However, such oxidative bromina-
tions involve the use of heavier metals in stoichiometric amounts
and often resulting in poor yields and selectivity (poor stereoselec-
tivity and unwanted side products). Most of the reported methods
for such transformation rely on modification of molecular bromine,
N-bromoimides, or metal salts with an oxidizing agent, while the
use of other reagents has been less investigated.8,9 In spite of the
variety of methods available for the preparation of vic-bromohy-
drins and dibromides directly from olefins, many of them often in-
volve the use of expensive reagents and the formation of mixture of
products resulting in low yields of the desired products. The
replacement of such reagents by non-toxic, mild, selective, and
easy-to-handle reagents is very desirable and represents an
important goal in the context of clean synthesis.
Classical bromination involves the use of hazardous elemental
bromine, which is a pollutant and generates hazardous HBr as
byproduct. The use of N-bromoimide is a better alternative for
molecular bromine, which does not produce HBr in the bromina-
tion of olefins, but they are expensive and generate organic waste.
Other drawbacks of these methods are low yield and long reaction
time.
OxoneÒ, a potassium triple salt containing potassium peroxy
monosulfate, is an effective oxidant. Due to its stability, water-sol-
ubility, ease of transport, non-toxic ‘green’ nature, non-polluting
byproducts, and cost-effectiveness, this solid reagent has become
an increasingly popular reagent for oxidative transformations.10–
14 OxoneÒ is a commonly used reagent (oxidant) for the conversion
of alkenes into epoxides.15
At present, oxidative bromination continues to be of great inter-
est because it precludes the use of volatile, hazardous bromine. A
In continuation of our interest on the halogenation reactions,
herein, we report a very simple, mild, and efficient method for
the direct synthesis of bromohydrins and dibromides from olefins
using NH4Br as a bromine source and oxoneÒ as an oxidant without
catalyst in a highly regio- and stereoselective fashion in short
⇑
Corresponding author. Tel.: +91 40 27191704; fax: +91 40 27160387/27160757.
E-mail address: narendern33@yahoo.co.in (N. Nama).
0040-4039/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2012.01.026

1402
A. K. Macharla et al. / Tetrahedron Letters 53 (2012) 1401–1405
reaction time (Scheme 1).16,17 Bromination of olefins using NH4Br
and oxoneÒ has not been studied so far.
Table 1
Optimization of the bromohydrins and dibromides
Initially, we investigated the bromohydroxylation of styrene
with NH4Br and oxoneÒ as the oxidant in various solvents such
as CH3CN, DCM, CCl4, acetone, and in combination with water (Ta-
ble 1, entries 1–17). The results obtained suggested that a mixture
of acetonitrile and water in 1:1 ratio was the best solvent system
for bromohydrin formation (Table 1, entry 10).
Stimulated by these affirmative preliminary results, we decided
to examine the NH4Br-oxoneÒ reagent system for hydroxybromin-
ation on a number of different activated, inactivated, and moder-
ately activated aromatic alkenes (Table 2, entries 2–7),
asymmetric trans-alkenes (Table 2, entries 10–14), cyclic, and lin-
ear alkenes (Table 2, entries 16–20) under similar reaction condi-
tions. Hydroxybromination of all olefins took place quickly and
completed in less than or equal to 5 min.
Olefin with highly activated arenes, that is, 4-methoxystyrene
produced the corresponding bromohydrin in excellent yield with-
out the formation of ring or dibrominated products (Table 2, entry
2). Olefins with moderately activated arenes (alkyl substituted),
that is, 4-methyl, 4-tert-butyl, and 2,4-dimethylstyrene yielded
the corresponding bromohydrins in moderate to high yields with-
out forming any side-chain and ring brominated products, but a
significant amount of dibromo product was observed (Table 2, en-
OH
Br
NH4Br, Oxone
Ph
+
Ph
Ph
Solvent
Br
Br
1
3
2
Entry
Solvent
Time
Yielda (%)
2
3
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
CH3CN
Acetone
DCM
CHCl3
CCl4
H2O
24 hb
24 hb
24 hb
24 hb
24 hb
2 minb
—
2
—
9
—
56
65
84
85
92
83
79
10
10
8
12
85
—
—
—
13
20
33
60
48
—
11
—
29
30
12
10
5
12
16
48
49
55
40
10
65
80
97
81
73
60
CH3CN/H2O (9:1)
CH3CN/H2O (4:1)
CH3CN/H2O (3:2)
CH3CN/H2O (1:1)
CH3CN/H2O (2:3)
CH3CN/H2O (1:4)
DCM/H2O (1:1)
DCM/H2O (1:1)
CHCl3/H2O (1:1)
CCl4/H2O (1:1)
Acetone/H2O (1:1)
CH3CN
CH3CN
CH3CN
CH3CN/H2O (10:0.25)
CH3CN/H2O (10:0.5)
CH3CN/H2O (10:1)
10 minb
10 minb
5 minb
2 minb
2 minb
2 minb
3 minb
30 minb
3 minb
3 minb
2 minb
5 hc
tries 3–5).
97% yield, whereas 4-chloro-
a
-Methylstyrene gave the respective bromohydrin in a
-methylstyrene afforded the corre-
a
sponding bromohydrin in an 84% yield, along with a substantial
amount (10%) of dibrominated product (Table 2, entries 8 and 9).
Regio- as well as stereoselective products were formed when
asymmetric trans-alkenes were subjected to bromohydroxylation
and selectively corresponding erythro isomers were obtained.
trans-Cinnamyl alcohol provided the corresponding erythro
bromohydrin in excellent yield (Table 2, entry 10). When the conju-
gated ketones, acids, and esters with a phenyl group at the b-posi-
tion were subjected to bromohydroxylation under similar reaction
24 hd
7 he
19 hd
1.3 hd
3 mind
a
b
c
Isolated yields.
Styrene (2 mmol), NH4Br (2.2 mmol), OxoneÒ (2.2 mmol), solvent (10 mL), rt.
Reflux temperature.
Styrene (2 mmol), NH4Br (4.4 mmol), OxoneÒ (2.2 mmol), solvent (10 mL), rt.
Reflux temperature.
d
e
conditions, furnished the corresponding erythro-b-hydroxy-
a-bro-
mo products accompanied by a significant amount of erythro-
a,b-
dibromo products (Table 2, entries 11–14).
Not only aromatic olefins, cyclic, and linear olefins also gave the
corresponding hydroxybrominated products in moderate to high
yields (Table 2, entries 16–20). 1-Methyl-1-cyclohexene and 3-
methyl-3-butene-1-ol exclusively yielded the Markovnikov’s
products (Table 2, entries 17 and 18), while with monosubstituted
linear olefin, a limited anti-Markovnikov product was also ob-
served. For example, 1-dodecene resulted in the formation of
Markovnikov product (1-bromododecan-2-ol) as well as anti-
Markovnikov product (2-bromododecan-1-ol) in 47% and 14%
yields, respectively (Table 2, entry 19). Mixed regioselectivity is ob-
served with linear asymmetric trans-alkene, that is, trans-2-octene
afforded the erythro-2-bromooctan-3-ol and erythro-3-bromooc-
tan-2-ol in the ratio of 25:36 (Table 2, entry 20).
From the investigated results of bromohydroxylation of styrene
in different solvents, we observed that acetonitrile turned out to be
the best solvent for the formation of respective dibrominated prod-
uct in terms of yield and reaction rates (Table 1, entry 1). Thus, we
investigated the dibromination of styrene with NH4Br and oxoneÒ
in CH3CN and in combination with H2O at room temperature and
reflux temperature (Table 1, entries 18–23). One equivalent of sty-
rene treated with 2.2 equiv of NH4Br and 1.1 equiv of oxoneÒ in
CH3CN at room temperature gave the corresponding dibrominated
product with an 80% yield in 24 h (Table 1, entry 14). Significant
improvement in yield and decrease in reaction time were achieved
by conducting the reaction at reflux temperature and yielded the
respective dibrominated product in a 97% yield within 7 h (Table
1, entry 20).
Bromohydroxylation of electron-deficient double bond in 1,4-
naphthoquinone and coumarin failed to react (Table 2, entries 21
and 22). The attempted bromohydroxylation of cholesterol and
After optimizing the reaction conditions, we have extended the
process to a variety of olefins, which are summarized in Table 2.
They were conveniently converted into their respective dibromides
cholest-4-ene-3-one resulted in
a
complex mixture, which
contained virtually no bromohydrin.
in excellent yields (in exception 4-methoxystyrene and a-methyl-
styrene provided a mixture of unidentified products (Table 2, en-
tries 2, 8 and 9)).
X
Dibromination of asymmetric trans-alkenes selectively formed
the corresponding erythro isomers (Table 2, entries 10–14). Cyclic
and linear alkenes furnished the corresponding dibrominated prod-
uct in excellent yields (Table 2, entries 16–20). In case of 1,4-naph-
thoquinone, instead of the expected dibrominated product, 2-
bromo-1,4-naphthoquinone was obtained in excellent yield
(Table 2, entry 21).
NH4Br, Oxone
RI
RI
R
R
CH3CN:H2O (1:1)
or CH3CN
Br
R = Alkyl / Aryl
X = OH / Br
RI = H / Alkyl / Aryl
Scheme 1. Hydroxybromination and dibromination of olefins.

A. K. Macharla et al. / Tetrahedron Letters 53 (2012) 1401–1405
1403
Table 2
Synthesis of Bromohydrins and Dibromides from Various Olefins
X
NH4Br, Oxone
RI
RI
4 : X = OH
5 : X = Br
R
R
CH3CN : H2O(1:1)/
CH3CN
Br
Entry
Olefin
Time
Product
Yielda (%)
4
5
R3
R3
X
Br
R2
R1
R1
R2
R1
R2
H
R3
H
1
H
2 minb
7 hc
92 (4a)
—
90 (4b)
79 (4c)
—
70 (4d)
—
66 (4e)
—
89 (4f)
—
89 (4g)
—
97 (4h)
84 (4i)
5 (5a)
97 (5a)
—
2
3
OMe
Me
H
H
H
H
1 minb
2 minb
5 hc
16 (5c)
95 (5c)
15 (5d)
92 (5d)
17 (5e)
0 (5e)
7 (5f)
96 (5f)
6 (5g)
90 (5g)
—
4
5
6
7
Me
tBu
Cl
Me
H
H
H
H
H
1 minb
4 hc
1 minb
6 hc
H
2 minb
13 hc
Br
H
3 minb
13 hc
8
9
H
Cl
H
H
Me
Me
2 minb
2 minb
10 (5i)
R4
X
Ph
R4
Ph
R4
Br
10
11
12
13
14
CH2OH
COCH3
COOH
COOMe
COPh
3 minb
12 hc
92e (4j)
—
5e (5j)
98e (5j)
15e (5k)
90e (5k)
10e (5l)
96e (5l)
27e (5m)
97e (5m)
30e (5n)
97e (5n)
3 minb
15 hc
77e (4k)
—
3 minb
13 hc
80e (4l)
—
4 minb
12 hc
63e (4m)
—
3 minb
13 hc
62e (4n)
—
X
15
16
17
1 minb
8.3 hc
86 (4o)
5 (5o)
Br
—
90 (5o)
X
3 minb
23 hd
85 (4p)
9 (5p)
Br
—
96 (5p)
X
1 minb
20 hd
89 (4q)
6 (5q)
Br
—
93 (5q)
X
HO
18
19
1 minb
4 hc
84 (4r)
9 (5r)
HO
Br
—
89 (5r)
X
CH3(CH2)9
2 minb
9 hc
47 (4s) (14)f (4sI)
33 (5s)
CH3(CH2)9
Br
—
97 (5s)
(continued on next page)

1404
A. K. Macharla et al. / Tetrahedron Letters 53 (2012) 1401–1405
Table 2 (continued)
Entry
Olefin
Time
Product
Yielda (%)
4
5
X
25e (4t)
CH3(CH2)4
20
21
1 minb
5 hc
30e (5t)
96e (5t)
(36)g (4tI)
CH3(CH2)4
O
Br
—
O
O
X
1 hb
5 hc
—
—
—
Br
O
X
—(97)h
(5u)
Br
O
22
1 hb
—
—
—
O
O
O
10 hc
23 (5v)
a
Isolated yields.
b
Olefin (2 mmol), NH4Br (2.2 mmol), OxoneÒ (2.2 mmol), CH3CN/H2O (1:1) (10 mL) at room temperature.
c
d
e
f
Olefin (2 mmol), NH4Br (4.4 mmol), OxoneÒ (2.2 mmol), CH3CN (10 mL) at reflux temperature.
At room temperature.
Only erythro products.
2-Bromododecan-1-ol.
erythro-3-Bromooctan-2-ol.
2-Bromo-1,4-naphthoquinone.
g
h
Table 3
Hydroxybromination and Dibromination of cis and trans-stilbene
To study the mechanism of the reaction (hydroxybromination/
dibromination), we carried out a blank experiment with styrene
and NH4Br in the absence of oxoneÒ under similar reaction condi-
tions and the reaction did not succeed. Thus, the role played by the
oxoneÒ (oxidant) was justified. The plausible reaction mechanism
for hydroxybromination and dibromination of olefins is shown in
Scheme 2 based on the literature18 and blank experiment. It is as-
sumed that oxidation of bromide ion by peroxymonosulfate ion
could give the hypobromite ion, which further undergoes electro-
philic addition onto the olefin to give a three-membered cyclic bro-
monium ion intermediate. The cyclic intermediate undergoes ring
Ph
X
Ph
Ph
X
NH4Br, Oxone
Solvent
6
Ph
Ph
+
Ph
Ph
Br
Br
8
9
Ph
7
( )
( )
2
Entry
Stilbene
Solvent
Time
X
Yield (%)a
opening by the nucleophile (hydroxy or bromide ion) via SN path
way to yield the anti vicinal hydroxybromo/dibromo substituted
product. The SN opening is responsible for high anti-stereoselec-
tivity of the bromo product. In all aromatic olefins, the incoming
nucleophile entered at the benzylic position of cyclic intermediate
exclusively. The regioselectivity (of aromatic olefins) can be ex-
8
9
2
1
2
3
4
6
7
6
7
CH3CN/H2O (1:1)
CH3CN/H2O (1:1)
CH3CN
5 minb
2 minb
20 hc
OH
,,
Br
,,
78 (8a)d
15d (8a)
80e (8b)
—
—
51f (9a)
—
CH3CN
16 hc
95f (9b)
a
plained by considering the fact that the
more positive than the b-position due to the presence of the aro-
matic ring. Nucleophilic opening of the cyclic bromonium interme-
diate is most likely from the more positive
stereochemistry of the products is confirmed by comparing the
1H NMR coupling constant data of protons attached to the carbons
bearing –OH/–Br and –Br groups of the bromohydrins/dibromides
with previously reported data.6–8,19
a-position (benzylic) is
Isolated yields.
Stilbene (2 mmol), NH4Br (2.2 mmol), OxoneÒ (2.2 mmol), Solvent (10 mL) at
b
room temperature.
c
Stilbene (2 mmol), NH4Br (4.4 mmol), OxoneÒ2.2 mmol), Solvent (10 mL) at
a-position. The
room temperature.
d
erythro Products.
meso Product.
threo Products.
e
f
The role of alkene geometry on the anti stereochemistry of the
addition was tested by conducting reactions with cis and trans-stil-
bene. Hydroxybromination and dibromination of cis-stilbene were
more rapid than its trans-isomer and both gave anti addition prod-
ucts. trans-Stilbene produced erythro hydroxybrominated (Table 3,
entry 1) and meso dibrominated products (Table 3, entry 3),
whereas cis-stilbene afforded the corresponding threo dibrominat-
ed product (Table 3, entry 4) (In case of hydroxybromination of
cis-stilbene, significant amount of corresponding erythro isomer
was also obtained (Table 3, entry 2)).
In conclusion, we have developed a mild and efficient method
for the regio- and stereoselective hydroxybromination and dibro-
mination of olefins using eco-friendly reagents in environmentally
benign and non-chlorinated solvents. Though oxoneÒ is known as a
best reagent (oxidant) for the epoxidation of olefins, we have not
observed any epoxidation products in this investigation. The
advantage of our system over other methods is that the use of a
catalyst is not required to enhance the reactivity of the reagents,
to control the regio- and stereoselectivities or to improve the yield.
The products are easily separated from the reagents and their

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1405
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Scheme 2. The plausible reaction mechanism.
byproducts. It is noteworthy that the present method provides a
new route for the bromohydroxylation of olefins.
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5911; (h) Ho, C.-Y.; Chen, Y.-C.; Wong, M.-K.; Yang, D. J. Org. Chem. 2005, 70,
898–906; (i) Hashimoto, N.; Kanda, A. Org. Process Res. Dev. 2002, 6, 405–406.
16. General procedure for the synthesis of bromohydrins: To a solution of olefin
(2 mmol) in CH3CN/H2O (1:1) (10 mL) were added NH4Br (2.2 mmol) and
OxoneÒ (2.2 mmol) and the mixture was stirred at room temperature for the
time shown in Table 2. After completion (as indicated by TLC), the reaction
mixture was filtered and the solvent evaporated under reduced pressure. The
products were purified by column chromatography (Hexane/EtOAc, 90:10)
over silica gel.
17. General procedure for the synthesis of dibromides: To a solution of olefin
(2 mmol) in CH3CN (10 mL) were added NH4Br (4.4 mmol) and OxoneÒ
(2.2 mmol) and the mixture was stirred at reflux temperature for the time
shown in Table 2. After completion (as indicated by TLC), the reaction mixture
was filtered and the solvent evaporated under reduced pressure. The products
were purified by column chromatography (Hexane/EtOAc, 98:2) over silica gel.
18. (a) Montgomery, R. E. J. Am. Chem. Soc. 1974, 96, 7820; (b) You, H. W.; Lee, K.-J.
Synlett 2001, 105–107; (c) Lee, K.-J.; Lim, K. W.; Chi, D. Y. Bull. Korean Chem. Soc.
2001, 22, 549–550.
M.A.K. thanks the CSIR, New Delhi, for the award of a Senior
Research Fellowship.
Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.tetlet.2012.01.026.
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