Regioselective hydroxyselenation of styrenes by diselenides using the Zn/AlCl3 System

Article abstract of DOI:10.1055/s-0029-1217081

A facile, zinc/aluminum(III) chloride promoted highly regioselective one-pot procedure has been developed for the preparation of β-hydroxy selenides from various styrenes and diselenides by Se-Se bond cleavage using the Zn/AlCl₃ system in aqueo

Full text of DOI:10.1055/s-0029-1217081

SHORT PAPER
33
Regioselective Hydroxyselenation of Styrenes by Diselenides Using the
Zn/AlCl3 System
Regioselective
H
a
n
ationof
a
S
tyrenes hman Movassagh,* Sepideh Farshbaf
Department of Chemistry, K. N. Toosi University of Technology, P. O. Box 16315-1618, Tehran, Iran
Fax +98(21)22853650; E-mail: bmovass1178@yahoo.com
Received 30 July 2009
OH
Abstract: A facile, zinc/aluminum(III) chloride promoted highly
Zn/AlCl3, O2
1)
3
Ar
SeR
RSe-SeR
1
regioselective one-pot procedure has been developed for the prepa-
ration of b-hydroxy selenides from various styrenes and diselenides
by Se–Se bond cleavage using the Zn/AlCl3 system in aqueous
acetonitrile and in the presence of oxygen.
[(RSe)2Zn]
Ar
MeCN, 80 °C
2) H2O, r.t., O2
2
4
Scheme 1
Key words: b-hydroxy selenides, diselenides, styrenes, regioselec-
tive, Zn/AlCl3 system
Simple stirring of diselenides 1 with metallic zinc dust in
the presence of aluminum(III) chloride in dry acetonitrile
at 80 °C produced the zinc selenolate 2. Then, the mixture
was cooled to room temperature followed by addition of
styrenes 3 and water, which gave, after workup, the de-
sired product 4 with yields ranging from 52–91%. Repre-
sentative results are summarized in Table 1. The results
show the regioselective addition of various diaryl dise-
lenides to several substituted styrenes in an anti-
Markovnikov fashion leading to the corresponding b-hy-
droxy selenides in good to high yields. The yields reported
in Table 1 are of the isolated major product. Generally, the
reaction goes to completion in a short time (0.5–3 h).
However, under these conditions, the much less reactive
cyclohexene (Table 1, entry 10) did not produce the ex-
pected product even after prolonged reaction times. When
the reaction was conducted under the same reaction con-
ditions, but under an inert (N2) atmosphere, no product
was obtained. This indicates that aerial oxygen is involved
in the hydroxyselenation of styrenes.15
b-Hydroxy selenides are potentially useful intermediates
in organic synthesis.1 They can be transformed into allyl
alcohols,1a,b,2 olefins,3–5 epoxides,6 halohydrins,7 and var-
ious oxygenated five- and six-membered heterocycles.8
They have also been utilized in C–C9 and C–N10 bond for-
mation reactions. Among several routes to b-hydroxy se-
lenides, ring opening of epoxides with selenolate anions,
which are generated from diselenides,1a,11 is the most
common. However, some of these methods suffer from
certain drawbacks, such as high or low temperatures, long
reaction times, unsatisfactory yields, and weak regiose-
lectivity. Hydroxyselenation reactions of alkenes via sele-
niranium ion intermediates is another method commonly
used for the straightforward synthesis of b-hydroxy se-
lenides.12 Recently, Zhang and co-workers13 reported the
synthesis of b-hydroxy selenides via thermal reaction of
alkyl aryl selenoxides in the presence of water in the su-
percage of zeolite NaY. However, various disadvantages
such as long reaction times, the use of low temperatures,
the unavailability of reagents, low to poor yields of prod-
ucts, and multistep procedures, etc, encountered in the re-
ported methodologies12,13 necessitate the development of
a more efficient and convenient method. Very recently,
we reported a new methodology for the synthesis of b-hy-
droxy sulfides from styrenes and disulfides using the zinc/
aluminum(III) chloride (Zn/AlCl3) system.14 We now find
that a one-pot reaction of selenolate anions, generated in
situ by reductive cleavage of diaryl diselenides in the
presence of Zn/AlCl3, with styrenes in aqueous acetoni-
trile at room temperature under an ambient atmosphere af-
fords b-hydroxy selenides in good to high yields
(Scheme 1). As far as we know, no investigation has been
reported using the reaction of selenolate anions (RSe–)
with styrenes for the synthesis of b-hydroxy selenides.
In summary, this zinc/aluminum(III) chloride promoted,
one-pot procedure for the addition of a selenolate anion
(RSe–) to styrenes takes place regioselectively giving b-
hydroxy selenides in an anti-Markovnikov manner. This
method offers significant advantages with regards to op-
eration, time, handling of catalysts, and cost and, thus,
presents an alternative to existing procedures. To our
knowledge, this is the first example of the reaction of se-
lenolate anions with styrenes for the synthesis of b-hy-
droxy selenides.
Melting points were recorded on a Buchi B-540 apparatus and are
uncorrected. IR spectra were recorded on an ABB FTLA 2000 in-
1
strument. H NMR (300 MHz) and 13C NMR (75 MHz) spectra
were recorded on a Bruker AQS-300 Avance spectrometer in
CDCl3 using TMS as an internal standard. MS were recorded on a
Hewlett-Packard 5973 mass spectrometer operating at 70 eV.
All known compounds are indicated as such (Table 1); for all novel
compounds IR, 1H and 13C NMR, and analytical data are supplied.
SYNTHESIS 2010, No. 1, pp 0033–0035
x
x
.
x
x
.2
0
0
9
Advanced online publication: 26.10.2009
DOI: 10.1055/s-0029-1217081; Art ID: Z16209SS
© Georg Thieme Verlag Stuttgart · New York

34
B. Movassagh, S. Farshbaf
SHORT PAPER
Table 1 Hydroxyselenation of Styrenes from Diselenides in the Presence of the Zn/AlCl3 System and Molecular Oxygen
Entry Styrene
R
Producta
Time (h) Yieldb (%) Regioselectivityc a/b
OH
a
1
Ph
4a
0.75
3
87
73
91
0:100
0:100
0:100
b
b
SePh
Cl
Cl
Cl
OH
a
b
2
Ph
Ph
4b16a
SePh
Cl
OH
a
3
4c6
0.5
SePh
SePh
OH
a
4
Ph
Ph
Ph
4d6
4e16b
4f
1.33
3
70
52
65
4:96
b
HO
Ph
Ph
a
b
5
6
0:100
13:87
Ph
SePh
Ph
OH
a
1.5
b
SePh
OH
a
7
8
4-ClC6H4
4-ClC6H4
4g
4h
0.5
80
86
12:88
16:84
b
Se
Cl
Cl
Cl
OH
a
0.75
2.5
b
b
Se
Se
Cl
Cl
OH
a
9
4-ClC6H4
Ph
4i
57
–
11:89
–
10
no reaction
–
24
a References are provided for known compounds.
b Isolated yields.
c Refers to the ratio of selenolate anion attack at carbon-a and carbon-b determined by 1H NMR analysis of the crude reaction mixture.
Hydroxyselenation of Styrenes by Diselenides Using the
Zn/AlCl3 System; General Procedure
2-(4-Chlorophenyl)-1-(phenylselanyl)propan-2-ol (4a)
IR (neat): 766, 828, 1484, 1579, 3456 cm–1 (br).
A mixture of diselenide (0.5 mmol), Zn dust (3.8 mmol), and anhyd
AlCl3 (2.25 mmol) was suspended in anhyd MeCN (15 mL). The
mixture was refluxed, with stirring, for 1.5 h, during which time the
zinc powder was almost consumed. Then, the mixture was cooled
to r.t., the styrene (2.0 mmol) was added in 1 portion and stirring
was continued for 1 h at r.t. followed by addition of H2O (2 mL);
stirring was continued for the time specified (Table 1) in air. On
completion of the reaction, the soln was filtered, MeCN was evap-
orated, and EtOAc (30 mL) was added; the mixture was washed
with H2O (2 × 20 mL) and the organic layer was dried (Na2SO4).
The solvent was evaporated under reduced pressure and the crude
mixture was purified by preparative TLC (silica gel, n-hexane–
EtOAc, 4:1).
1H NMR (300 MHz, CDCl3): d = 1.62 (s, 3 H, CH3), 2.90 (br s, 1 H,
OH), 3.33 (d, J = 12.4 Hz, 1 H, CH2Se), 3.55 (d, J = 12.4 Hz, 1 H,
CH2Se), 7.19–7.28 (m, 5 H, Harom), 7.35 (d, J = 8.8 Hz, 2 H, Harom),
7.43–7.47 (m, 2 H, Harom).
13C NMR (75 MHz, CDCl3): d = 29.8, 45.0, 73.4, 126.3, 127.2,
128.3, 129.1, 130.1, 132.9, 133.1, 144.9.
MS (EI, 70 eV): m/z (%) = 328 (4) [M + 4]+, 326 (8) [M + 2]+, 324
(4) [M]+, 172 (87), 170 (42), 157 (32), 155 (66), 91 (36), 77 (25), 51
(19), 43 (100).
Anal. Calcd for C15H15ClOSe: C, 55.32; H, 4.64. Found: C, 55.6; H,
4.7.
Synthesis 2010, No. 1, 33–35 © Thieme Stuttgart · New York

SHORT PAPER
Regioselective Hydroxyselenation of Styrenes
35
1-(4-Methylphenyl)-2-(phenylselanyl)ethanol (4f)
Acknowledgment
IR (neat): 691, 736, 819, 1437, 1478, 1514, 1578, 3394 cm–1 (br).
Acknowledgment is made to the K. N. Toosi University of Techno-
logy Research Council, and Iranian National Science Foundation
(INSF, Grant No 86063/21) for financial support of this work.
1H NMR (300 MHz, CDCl3): d = 2.36 (s, 3 H, CH3), 2.79 (br s, 1 H,
OH), 3.17 (dd, J = 12.7, 9.2 Hz, 1 H, CH2Se), 3.31 (dd, J = 12.7, 3.8
Hz, 1 H, CH2Se), 4.75 (dd, J = 9.2, 3.8 Hz, 1 H, CHOH), 7.16 (d,
J = 8.0 Hz, 2 H, Harom), 7.25 (d, J = 8.0 Hz, 2 H, Harom), 7.28–7.34
(m, 3 H, Harom), 7.54–7.58 (m, 2 H, Harom).
13C NMR (75 MHz, CDCl3): d = 21.1, 38.4, 72.2, 125.7, 127.3,
129.2, 129.3, 130.0, 133.1, 137.7, 139.6.
References
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Int. Ed. Engl. 1974, 13, 804. (c) Seebach, D.; Beck, A. K.
Angew. Chem., Int. Ed. Engl. 1974, 13, 805.
MS (EI, 70 eV): m/z (%) = 292 (21) [M + 2]+, 290 (11) [M]+,172
(100), 170 (49), 121 (82), 91 (95), 77 (61), 65 (30), 51 (25), 43 (23).
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Anal. Calcd for C15H16OSe: C, 61.86; H, 5.54. Found: C, 62.3; H,
5.6.
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2-(4-Chlorophenyl)-1-(4-chlorophenylselanyl)propan-2-ol (4g)
Colorless crystals; mp 63–65 °C.
IR (neat): 813, 1474, 1489, 3449 cm–1 (br).
1H NMR (300 MHz, CDCl3): d = 1.62 (s, 3 H, CH3), 2.78 (br s, 1 H,
OH), 3.28 (d, J = 12.6 Hz, 1 H, CH2Se), 3.52 (d, J = 12.6 Hz, 1 H,
CH2Se), 7.17 (d, J = 8.4, 2 H, Harom), 7.26 (d, J = 8.4 Hz, 2 H,
Harom), 7.34 (d, J = 8.4 Hz, 2 H, Harom), 7.36 (d, J = 8.4 Hz, 2 H,
(6) Dumont, W.; Krief, A. Angew. Chem., Int. Ed. Engl. 1975,
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1999, 55, 14097. (d) Gruttadauria, M.; Lo Meo, P.; Noto, R.
Tetrahedron 1999, 55, 4769. (e) Gruttadauria, M.; Lo Meo,
P.; Noto, R. Tetrahedron Lett. 1999, 40, 8477.
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Pharm. Bull. 1981, 29, 105. (b) Kametani, T.; Kurobe, H.;
Nemoto, H. J. Chem. Soc., Perkin Trans. 1 1981, 756.
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H
arom).
13C NMR (75 MHz, CDCl3): d = 29.8, 45.3, 73.4, 126.3, 128.3,
128.4, 129.2, 133.0, 133.6, 134.5, 144.7.
MS (EI, 70 eV): m/z (%) = 364 (1) [M + 6]+, 362 (3) [M + 4]+, 360
(5) [M + 2]+, 358 (2) [M]+, 208 (30), 206 (64), 204 (30), 155 (94),
91 (14), 75 (16), 43 (100).
Anal. Calcd for C15H14Cl2OSe: C, 50.03; H, 3.92. Found: C, 50.1;
H, 4.0.
1-(4-Chlorophenylselanyl)-2-phenylpropan-2-ol (4h)
IR (neat): 701, 765, 811, 1446, 1474, 3455 cm–1 (br).
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1H NMR (300 MHz, CDCl3): d = 1.66 (s, 3 H, CH3), 2.81 (br s, 1 H,
OH), 3.33 (d, J = 12.5 Hz, 1 H, CH2Se), 3.58 (d, J = 12.5 Hz, 1 H,
CH2Se), 7.17 (d, J = 8.5 Hz, 2 H, Harom), 7.23–7.51 (m, 7 H, Harom).
13C NMR (75 MHz, CDCl3): d = 29.8, 45.4, 73.7, 124.7, 127.1,
128.3, 128.7, 129.2, 133.3, 134.3, 146.2.
MS (EI, 70 eV): m/z (%) = 328 (7) [M + 4]+, 326 (14) [M + 2]+, 324
(9) [M]+, 208 (19), 206 (42), 204 (23), 121 (78), 91 (13), 77 (19), 51
(10), 43 (100).
Anal. Calcd for C15H15ClOSe: C, 55.32; H, 4.64. Found: C, 55.2; H,
5.0.
2-(4-Chlorophenylselanyl)-1-phenylethan-2-ol (4i)
IR (neat): 701, 766, 813, 1453, 1474, 3417 cm–1 (br).
1H NMR (300 MHz, CDCl3): d = 2.73 (br s, 1 H, OH), 3.16 (dd,
J = 12.7, 9.0 Hz, 1 H, CH2Se), 3.29 (dd, J = 12.7, 4.0 Hz, 1 H,
CH2Se), 4.77 (dd, J = 9.0, 4.0 Hz, 1 H, CHOH), 7.25 (d, J = 8.6 Hz,
2 H, Harom), 7.30–7.36 (m, 5 H, Harom), 7.47 (d, J = 8.6 Hz, 2 H,
Harom).
13C NMR (75 MHz, CDCl3): d = 38.6, 72.4, 125.8, 127.5, 128.1,
128.6, 129.4, 133.7, 134.5, 142.3.
MS (EI, 70 eV): m/z (%) = 314 (20) [M + 4]+, 312 (51) [M + 2]+,
310 (20) [M]+, 208 (23), 206 (53), 204 (27), 107 (84), 91 (27), 79
(100), 51 (34), 43 (37).
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N. J. Chem. Soc., Chem. Commun. 1988, 111.
Anal. Calcd for C14H13ClOSe: C, 53.95; H, 4.20. Found: C, 54.4; H,
4.1.
Synthesis 2010, No. 1, 33–35 © Thieme Stuttgart · New York