Synthesis of bromo- And iodohydrins from deactivated alkenes by use of N-Bromo- and W-iodosaccharin

Article abstract of DOI:10.1002/ejoc.200400829

N-Bromo and N-iodosaccharin react with electron-deficient alkenes such as α,β-unsaturated ketones, acids, esters and nitriles in aqueous organic solvents, yielding the corresponding halohydrins in good yields. The reactions take place at room temperature,

Full text of DOI:10.1002/ejoc.200400829

FULL PAPER
Synthesis of Bromo- and Iodohydrins from Deactivated Alkenes by Use of
N-Bromo- and N-Iodosaccharin[‡]
Damijana Urankar,[a] Irena Rutar,[a,b] Barbara Modec,[a] and Darko Dolenc*[a]
Keywords: Bromohydrins / Iodohydrins / Enones / Halogenation
N-Bromo and N-iodosaccharin react with electron-deficient
alkenes such as α,β-unsaturated ketones, acids, esters and
room temperature, mostly within short reaction times and
with high anti stereoselectivity.
nitriles in aqueous organic solvents, yielding the correspond- (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
ing halohydrins in good yields. The reactions take place at
Germany, 2005)
saccharin was the last to be described in the literature, it has
already found some application in the field of iodination
of organic compounds.[23,24,25] Introduction of iodine as an
electrophile into deactivated alkenes is particularly difficult,
and reactive iodination reagents such as N-iodosaccharin
could prove suitable for this purpose.
This paper describes the results of bromination and io-
dination of some electron-deficient alkenes (e.g., enones, cy-
anoalkenes and haloalkenes) by N-bromo- and N-iodosac-
charin (NBSac and NISac) in aqueous or alcoholic media.
Introduction
Halohydrins are valuable reaction intermediates that can
be transformed into epoxides,[1] ketones[2] and other deriva-
tives.[3–5] Conversely, epoxides are also frequently opened to
form halohydrins. This is achieved by the use of hydrogen
halides or other reagents.[6–8] Halohydrins can also be syn-
thesized by a variety of methods other than from epoxides,
most often by functionalization of alkenes with appropriate
reagents including, among others, hypohalous acids or ele-
mental halogens in water,[1,9,10] halogens or halides used
together with oxidants,[11–13] interhalogen compounds,[14]
iodine(i) compounds (e.g., I(Py)2BF4),[15] bromates or io-
dates(v) in combination with NaHSO3.[16] Halohydrins can
also be obtained enantioselectively, with the aid of intra-
molecular or external chiral auxiliaries.[17,18] N-Haloamides
are also versatile reagents for converting alkenes into the
corresponding halohydrins.[9,19–22]
Functionalization of electron-rich double bonds presents
no problem, regarding the choice of reagents or reaction
times. In contrast, electrophilic additions to electron-poor
alkenes might be very slow, or might even not take place at
all. In such cases, strongly electrophilic reagents are re-
quired. Among the haloamides, the most popular of these
are N-halosuccinimides, which are moderately reactive, but
the electrophilicity of such compounds can be enhanced by
replacement of one (or both) carbonyl group(s) with sulfo-
nyl groups. N-Halosaccharins belong to one such class of
reagents. All four N-halosaccharins are known, but their
applicability has yet to be fully explored. Although N-iodo-
Results and Discussion
N-Iodo- and N-bromosaccharin react with α,β-unsatu-
rated ketones, acids or esters at room temperature in mix-
tures of acetonitrile or acetone and water, to yield the corre-
sponding halohydrins. The stereochemistry of the addition
is predominantly anti, so addition to (E)-alkenes results in
the formation of halohydrins with erythro or (mostly) like
(l) configuration.[26] Aqueous acetone reacts slowly with the
halogenating agent, thus limiting the applicability of this
solvent to relatively fast reactions.[27]
Brominations take place very quickly; the reactions are
typically complete within a few minutes at room tempera-
ture and concentrations of each reactant of approx. 1 m.
The exception is the nitrile (1g), which was converted into
the corresponding bromohydrin in two days. Brominations
of related compounds with N-bromosuccinimide (NBS)
were reported to be substantially slower.[28] Our preliminary
estimation, made by NMR, of the rates of bromination of
benzylideneacetone (1a) in [D4]MeOH with NBS and with
NBSac revealed that the reactivity of the latter is approxi-
mately 400 times that of the former. Bromination of benzyl-
ideneacetophenone (1b) and methyl (E)-cinnamate (1f) with
NBS in 10% excess required approx. 48 hours to achieve
the complete conversion of the starting alkene, with a yield
comparable to that attained with NBSac.
[‡] Presented in part at the national meeting “Slovenski kemijski
dnevi 2002” Maribor, Slovenia, September 2002. Book of ab-
stracts, pp. 197–200.
[a] University of Ljubljana, Faculty of Chemistry and Chemical
Technology,
Asˇkercˇeva 5, 1000 Ljubljana, Slovenia
Fax: +386-1-2419-220
E-mail: darko.dolenc@fkkt.uni-lj.si
ˇ
[b] Present address: Solski Center Nova Gorica,
Delpinova 9, 5000 Nova Gorica, Slovenia
Eur. J. Org. Chem. 2005, 2349–2353
DOI: 10.1002/ejoc.200400829
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D. Urankar, I. Rutar, B. Modec, D. Dolenc
FULL PAPER
Figure 1. Top: An ORTEP picture of 3c, drawn with 50% prob-
ability displacement ellipsoids and with hydrogen atoms shown as
arbitrarily sized spheres. Bottom: The molecules in 3c are associ-
ated by weak hydrogen bonding interactions into infinite chains
that propagate along the b axis. Each molecule is linked to two
neighbouring ones: to one through a pair of hydrogen bonds
formed between carbonyl oxygens and phenyl protons, with lengths
O(2)···C(12)i = 3.289(3) Å ((i) 2 –x, 1 –y, 1 –z), and to another
through a pair of hydrogen bonds formed between methoxy oxy-
gens and phenyl protons, with lengths O(1)···C(16)ii = 3.434(3) Å
((ii) 2 –x, –y, 1 –z).
Scheme 1.
Under similar conditions, iodinations are slower, the re-
actions usually being complete after several hours. Again,
related iodinations with N-iodosuccinimide are reported to
be considerably slower or even not to take place at all.[22]
Iodination of benzylideneacetophenone (1b) in methanol
or ethanol resulted in the formation of the corresponding
α-iodo-β-methoxy(3c) or β-ethoxy-α-iodoketone (3d).
The melting points of our methoxy (3c) and ethoxy (3d)
compounds differ substantially from the literature values.[29]
As there was a minor chance that we had obtained an
(R*,S*) isomer instead of the expected (R*,R*) form, a
structure determination of our product 3c by X-ray diffrac-
tion was carried out, confirming that the compound was
the (R*,R*) isomer.[30]
Bromination of (E)-1-bromo-1,2-diphenylethene (1i) in
acetonitrile/water yielded 2-bromo-1,2-diphenylethanone
(2i) as the only product.[31] This transformation could be
explained by the formation of an unstable bromohydrin
(4i), which in turn eliminates HBr, forming 2i.[32]
Aliphatic enones were brominated rapidly, yielding the
corresponding α-bromo-β-hydroxyketones. Bromination of
cyclohex-2-ene-1-one (1j) resulted in the formation of trans- Scheme 2.
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Eur. J. Org. Chem. 2005, 2349–2353

Bromo- and Iodohydrins from Deactivated Alkenes by Use of N-Bromo- and N-Iodosaccharin
FULL PAPER
Table 1. Bromination and iodination of alkenes with N-bromo- and were isolated, after completion of each reaction, by washing
N-iodosaccharin.[a]
the ether solutions of the reaction mixtures with aqueous
solutions of one equivalent of sodium hydrogen carbonate.
Conclusions
In conclusion, we can report that N-bromo- and N-iodo-
saccharin are potent halogenating reagents suitable for in-
troduction of halogen atoms into relatively unreactive, elec-
tron-poor alkenes, such as enones and related compounds.
The reactions proceed with high anti stereoselectivity in
short reaction times and under mild conditions, not affect-
ing other functional groups present, such as esters or ni-
triles.
Experimental Section
General: Solvents and reagents (Fluka, Aldrich, Merck) were used
as purchased. N-Bromosaccharin[34] and N-iodosaccharin[23] were
prepared by the published procedures. (Z)-1-Bromo-1,2-diphenyl-
ethene was synthesized from trans-stilbene.[35] NMR spectra were
measured on a Bruker Avance 300 DPX spectrometer (300 MHz)
with tetramethylsilane as internal standard, IR spectra on a BIO-
RAD Excalibur FT-IR spectrometer, mass spectra on a VG-Ana-
lytical Autospec EQ or a Hewlett–Packard HP 6890 GC-MS com-
bination. Elemental analyses were performed with a Perkin–Elmer
2400 CHN Analyser. Crystallographic data were collected on a
Nonius Kappa CCD diffractometer with use of monochromated
Mo-Kα radiation. The crystal was directly mounted on a dif-
fractometer under a stream of cold nitrogen gas.
Typical Procedure for Bromination and Iodination of Alkenes: The
alkene (1.0 mmol), the N-halosaccharin (1.1 mmol) and the solvent
(1–2 mL) were stirred at room temperature until the complete con-
version of a starting alkene. The reaction mixture was diluted with
diethyl ether and transferred into a separating funnel. The organic
layer was washed with a solution of sodium hydrogen carbonate
and sodium thiosulfate and then with water and was dried with
anhydrous sodium sulfate. The solvent was evaporated at reduced
pressure and the resulting product was purified by crystallization
or column chromatography.
[a] Reactions carried out at room temperature in mixtures of ace-
tone or acetonitrile and water (4:1), unless stated otherwise. [b] Iso-
lated yield (in parentheses after purification by crystallization or
chromatography). [c] Ref.[16] [d] Brominated with NBS. [e] In meth-
(2R*,3R*)-2-Bromo-3-hydroxy-1,3-diphenylpropan-1-one (2b): M.p.
anol. [f] In ethanol. [g] See Experimental Section.
84–85 °C. 1H NMR (CDCl3):[36] δ = 3.51 (d, J = 5.1 Hz, 1 H), 5.22
(d, J = 8.3 Hz, 1 H), 5.33 (dd, J = 8.3, 5.1 Hz, 1 H), 7.33–8.02 (m,
10 H) ppm. 13C NMR (CDCl3): δ = 47.9, 74.8, 127.3, 128.4, 128.6,
128.8, 129.0, 134.1, 134.6, 139.4, 194.6 ppm.
2-bromo-3-hydroxycyclohexan-1-one (2j), accompanied by
a small amount of compound with similar NMR and mass
spectrum, most probably a stereo- or regioisomer. Chroma-
tographic purification (silica, Et2O + hexane) gave reason-
ably pure 2j.
The attempted bromination of cholest-4-en-3-one re-
sulted in a complex mixture, which contained virtually no
bromohydrin.
Since saccharin, formed in the halogenation reactions, is
a moderately strong acid (pKa = 2.32),[33] it can easily be
removed after the reaction by washing the reaction mixture
with aqueous hydrogen carbonate or even with a weaker
base. Because it is a stronger acid than the majority of car-
boxylic acids, it can be removed selectively from a reaction
(2R*,3R*)-2-Bromo-3-hydroxy-3-phenylpropanoic Acid(2e): After
the complete conversion of starting trans-cinnamic acid, the reac-
tion mixture was diluted with diethyl ether and washed with an
aqueous solution of 1 equivalent of sodium hydrogen carbonate.
The organic phase was dried and the solvent was evaporated. M.p.
121–123 °C (lit.[37] 125 °C). 1H NMR ([D6]acetone):[38] δ = 4.39 (d,
J = 9.4 Hz, 1 H), 5.04 (d, J = 9.4 Hz, 1 H), 7.31–7.50 (m, 5 H) ppm.
13C NMR ([D6]acetone): δ = 49.7, 75.8, 128.4, 128.97, 129.01,
141.7, 170.2 ppm.
Methyl (2R*,3R*)-2-Bromo-3-hydroxy-3-phenylpropanoate (2f):
1
M.p. 57–59 °C (lit.[39] 62 °C). H NMR (CDCl3):[22] δ = 3.25 (s, 1
H), 3.80 (s, 3 H), 4.38 (d, J = 8.3 Hz, 1 H), 5.08 (d, J = 8.3 Hz, 1
H), 7.26–7.40 (m, 5 H) ppm. 13C NMR (CDCl3): δ = 47.5, 53.2,
mixture containing a carboxylic acid. The acids 2e and 3e 75.3, 127.0, 128.6, 128.8, 139.0, 169.9 ppm.
Eur. J. Org. Chem. 2005, 2349–2353
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© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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D. Urankar, I. Rutar, B. Modec, D. Dolenc
(2R*,3S*)-2-Bromo-3-hydroxy-3-phenylpropanenitrile (2g): M.p. product was purified by column chromatography (silica, diethyl
FULL PAPER
1
70–72 °C. H NMR (CDCl3): δ = 2.78 (d, J = 3.9 Hz, 1 H), 4.47
(d, J = 4.3 Hz, 1 H), 5.06 (dd, J = 4.3, 3.9 Hz, 1 H), 7.26–7.46 (m,
5 H) ppm. 13C NMR (CDCl3): δ = 34.4, 75.0, 114.9, 126.4, 128.9,
ether/hexane, 1:2) and crystallized from dichloromethane/hexane,
1
M.p. 100–102 °C. H NMR (CDCl3): δ = 2.8 (br.s, 1 H), 4.45 (d,
J = 4.6 Hz, 1 H), 4.96 (d, J = 4.6 Hz, 1 H), 7.4 (m, 5 H) ppm. 13C
129.6, 137.01. IR (KBr disc): ν = 3420 (OH), 2259 (CN) cm–1. MS NMR (CDCl3): δ = 5.8, 75.5, 116.8, 126.3, 128.8, 129.4, 137.8 ppm.
˜
(m/z (%)): 227 [M + 2]+ (1), 225 [M+] (1), 129 (7), 107 (100), 79 IR (KBr disc): ν = 3417 (OH), 2250 (CN) cm–1. MS (m/z (%)): 273
˜
(52), 77 (32), 51 (15). C9H8BrNO (226.07): C 47.82, H 3.57, N 6.20;
found C 47.52, H 3.64, N 6.57.
[M]+ (1), 166 (2), 127 (8), 107 (100), 91 (20), 79 (53), 77 (37).
C9H8INO (273.07): C 39.59, H 2.95, N 5.12; found C 39.75, H
3.03, N 4.97.
trans-2-Bromo-3-hydroxycyclohexanone (2j):[40] Oil, 1H NMR
(CDCl3): δ = 1.64 (m, 1 H), 1.82 (m, 1 H), 2.08 (m, 1 H), 2.38 (m,
2 H), 2.6 (br.s, 1 H), 2,75 (m, 1 H) 4.00 (ddd, J = 3.6, 7.0, 7.5 Hz,
1 H), 4.40 (dd, J = 1.1, 7.0 Hz, 1 H) ppm. 13C NMR (CDCl3): δ =
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20.1, 30.6, 38.7, 61.7, 75.2, 200.5 ppm. IR (liquid film): ν = 3439
˜
(OH), 1720 (CO) cm–1. MS (m/z (%)): 194 [M + 2]+ (1), 192 [M]+
(1), 134 (14), 113 (100), 95 (22), 71 (65), 60 (75), 43 (31).
(3R*,4R*)-4-Hydroxy-3-iodo-4-phenylbutan-2-one (3a): M.p. 63.7–
65.5 °C. H NMR (CDCl3): δ = 2.46 (s, 3 H), 3.4 (d, J = 5.2 Hz, 1
1
H), 4.71 (d, J = 8.5 Hz, 1 H), 5.10 (dd, J = 5.1, 8.5 Hz, 1 H), 7.4
(m, 5 H) ppm. 13C NMR (CDCl3): δ = 27.4, 35.5, 75.8, 127.0,
128.5, 128.6, 139.7, 203.9 ppm. IR (KBr disc): ν = 3406 (OH), 1704
˜
(CO) cm–1. MS (m/z (%)): 290 [M]+ (0.5), 230 (14), 184 (100), 163
(38), 107 (72), 105 (20), 103 (39), 91 (23), 79 (47), 77 (45).
C10H11IO2 (290.10): C 41.40, H 3.82; found C 41.40, H 3.65.
(2R*,3R*)-3-Hydroxy-2-iodo-1,3-diphenylpropan-1-one (3b): M.p.
122–124 °C. 1H NMR (CDCl3): δ = 3.8 (br.s, 1 H), 5.36 (d, J =
8.0 Hz, 1 H), 5.54 (d, J = 8.0 Hz, 1 H), 7.3–7.6 (m, 8 H), 8.0 (m,
2 H) ppm. 13C NMR (CDCl3): δ = 29.1, 76.0, 127.2, 128.46, 128.52,
128.73, 128.78, 134.0, 134.2, 139.9, 196.1 ppm. IR (KBr disc): ν =
˜
3482 (OH), 1661 (CO) cm–1. MS (m/z (%)): 246 (82), 225 (30), 207
(19), 105 (100), 91 (19), 77 (72). C15H13IO2 (352.17): C 51.16, H
3.72; found C 51.03, H 3.77.
[12] B. F. Sels, D. E. De Vos, P. A. Jacobs, J. Am. Chem. Soc. 2001,
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[18] S. A. Boyes, A. T. Hewson, J. Chem. Soc. Perkin Trans. 1 2000,
2759–2765.
(2R*,3R*)-2-Iodo-3-methoxy-1,3-diphenylpropan-1-one
(3c):
M.p.86–87 °C (lit.[28] 96 °C). H NMR (CDCl3): δ = 3.20 (s, 3 H),
4.90 (d, J = 10.1 Hz, 1 H), 5.39 (d, J = 10.1 Hz, 1 H), 7.3–7.6 (m,
8 H), 8.0–8.1 (m, 2 H) ppm. 13C NMR (CDCl3): δ = 28.6, 58.0,
84.2, 128.27, 128.30, 128.67, 128.75, 128.80, 133.5, 134.8, 138.5,
194.2 ppm. MS (m/z (%)): 366 [M]+(0.1), 239 (64), 230 (18), 223
(24), 207 (25), 121 (59), 105 (100), 103 (35), 91 (31), 77 (88).
1
(2R*,3R*)-3-Ethoxy-2-iodo-1,3-diphenylpropan-1-one (3d): M.p.
97–99 °C (lit.[28] 75–76 °C). 1H NMR (CDCl3): δ = 0.98 (t, J =
7.0 Hz, 3 H), 3.38 (m, 2 H), 5.00 (d, J = 10.2 Hz, 1 H), 5.37 (d, 1
H, J = 10.2 Hz, 1 H), 7.3–7.6 (m, 8 H), 8.0–8.1 (m, 2 H) ppm. 13C
NMR (CDCl3): δ = 15.1, 29.2, 65.9, 82.6, 128.2, 128.6, 128.7, 133.4,
135.0, 139.3, 194.1 ppm.
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(2R*,3R*)-3-Hydroxy-2-iodo-3-phenylpropanoic Acid (3e): Isolation
1
procedure: see 2e. M.p. 136–138 °C (lit.[41] 141–142 °C). H NMR
([D6]acetone):[14] δ = 4.54 (d, J = 9.7 Hz, 1 H), 5.06 (d, J = 9.7 Hz,
1 H), 7.3–7.5 (m, 5 H) ppm. 13C NMR ([D6]acetone): δ = 27.2,
76.8, 128.3, 128.91, 128.93, 142.2, 171.9 ppm.
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alkenes have erythro configurations. The more precise like/un-
like or (R*,S*) notation is compound-specific and it yields dif-
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[27] With long reaction times in acetone as a solvent, the excess of
the reagent was consumed and a product with lachrimatory
vapours appeared. This was not investigated further, but most
probably a haloacetone was formed.
Methyl (2R*,3R*)-3-Hydroxy-2-iodo-3-phenylpropanoate (3f): M.p.
1
60–62 °C. H NMR (CDCl3): δ = 3.4 (d, J = 5.8 Hz, 1 H), 3.77 (s,
3 H), 4.58 (d, J = 8.3 Hz, 1 H), 5.09 (dd, J = 5.8, 8.3 Hz, 1 H), 7.4
(m, 5 H) ppm. 13C NMR (CDCl3): δ = 24.9, 53.5, 76.7, 127.4,
129.0, 129.2, 139.8, 172.1 ppm. IR (KBr disc): ν = 3441 (OH), 1710
˜
(CO). MS (m/z (%)): 306 [M]+ (4), 200 (78), 179 (10), 168 (15), 107
(100), 91 (32), 79 (50), 77 (41). C10H13IO3 (308.12): C 39.24, H
3.62; found C 39.24, H 3.44.
(2R*,3S*)-3-Hydroxy-2-iodo-3-phenylpropanenitrile (3g): The reac-
tion was conducted for 5 days at approx. 40 °C with a 20% excess
of NISac, until the conversion of starting nitrile reached 60%. The
2352
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Bromo- and Iodohydrins from Deactivated Alkenes by Use of N-Bromo- and N-Iodosaccharin
FULL PAPER
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were added in calculated positions. Crystal data for 3c:
[32]
[33]
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[35]
[36]
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¯
C16H15IO2, Mr = 366.18, triclinic, space group P1, a =
6.9967(2). b = 9.5820(2), c = 11.4778(3) Å, α = 72.7315(11), β [37] P. D. de la Mare, M. A. Wilson, J. Chem. Soc. Perkin Trans. 2
= 85.6043(10), γ = 89.2023(11)o, V = 732.62(3) Å3, Z = 2, T =
1973, 653–656.
150(2) K, μ(Mo-Kα) = 2.181 mm–1, 5823 reflections measured, [38] M. Brink, E. Schjånberg, Spectrochimica Acta 1977, 33A, 1–5.
3255 unique (Rint = 0.0163). From all data the final R1 and
wR2 factors are 0.0247 and 0.0573. CCDC-241543 contains the
supplementary crystallographic data for this paper. These data
can be obtained free of charge from the Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
[31] The transformation of a vinyl bromide into an α-bromoketone
can also be achieved by the action of phenylselenenyl chloride
[39] M. A. Wilson, P. D. Woodgate, J. Chem. Soc. Perkin Trans. 2
1976, 141–147.
[40] G. Righi, P. Bovicelli, A. Sperandio, Tetrahedron Lett. 1999,
40, 5889–5892.
[41] E. L. Jackson, L. Pasiut, J. Am. Chem. Soc. 1928, 50, 2249–
2260.
Received: November 22, 2004
Eur. J. Org. Chem. 2005, 2349–2353
www.eurjoc.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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