Synthesis of β-hydroxy selenides using benzeneselenol and oxiranes under supramolecular catalysis in the presence of β-cyclodextrin in water

Article abstract of DOI:10.1016/j.tetlet.2005.10.094

A simple and efficient method for the synthesis of β-hydroxy selenides is reported at room temperature in impressive yields for the first time by the highly the regioselective ring-opening of oxiranes with benzeneselenol in water under supramolecular cata

Full text of DOI:10.1016/j.tetlet.2005.10.094

Tetrahedron
Letters
Tetrahedron Letters 46 (2005) 8837–8839
Synthesis of b-hydroxy selenides using benzeneselenol and
oxiranes under supramolecular catalysis in the presence of
b-cyclodextrin in water
R. Sridhar, B. Srinivas, K. Surendra, N. Srilakshmi Krishnaveni and K. Rama Rao*
Organic Chemistry Division-I, Indian Institute of Chemical Technology, Hyderabad 500 007, India
Received 12 August 2005; revised 13October 2005; accepted 19 October 2005
Available online 7 November 2005
Abstract—A simple and efficient method for the synthesis of b-hydroxy selenides is reported at room temperature in impressive
yields for the first time by the highly the regioselective ring-opening of oxiranes with benzeneselenol in water under supramolecular
catalysis in the presence of b-cyclodextrin. This is a direct one-pot synthesis of b-hydroxy selenides under mild conditions using
water as solvent and has many advantages over the existing methodologies. b-Cyclodextrin can also be recovered and reused.
Ó 2005 Elsevier Ltd. All rights reserved.
b-Hydroxy selenides are highly valuable intermediates in
organic synthesis1 due to their potential for transforma-
tion into allylic alcohols, olefins, epoxides, halohydrins,
oxygenated five- and six-membered hetreocycles, etc.2–5
Consequently, a number of methodologies have been
developed for the synthesis of b-hydroxy selenides.6
Most of the syntheses of b-hydroxy selenides involve
ring-opening of epoxides with diselenide by the in situ
formation of selenolate anions in the presence of metal
catalysts with poor yields and low regioselectivities in
certain cases.6a,b
selectivity. They catalyze reactions by supramolecular
catalysis involving reversible formation of host–guest
complexes via non-covalent bonding as seen in enzymes.
Complexation depends on the size, shape and hydro-
phobicity of the guest molecule. Thus, mimicking of bio-
chemical selectivity through orientation of the substrate
by complex formation positioning only certain regions
for favorable attack will be superior to chemical selectiv-
ity, which typically involves random attack. Our earlier
studies in the field of biomimetic modelling of organic
chemical reactions involving cyclodextrins8 prompted
us to attempt the regioselective ring opening of oxiranes
with benzeneselenol under biomimetic conditions using
cyclodextrins in water as the solvent at room tempera-
ture (Scheme 1).
In view of these limitations, there is still a need for the
development of clean procedures for the synthesis of
b-hydroxy selenides via ring opening of oxiranes directly
with benzeneselenol in water in the presence of a recycla-
ble catalyst and without using any harmful organic sol-
vents; water is safe, economical and environmentally
benign.7 To achieve these ideal conditions, the best
choice appeared to be through supramolecular catalysis
involving cyclodextrins.
In general, the reaction was carried out by the in situ for-
mation of the b-CD complex of the oxirane in water fol-
lowed by the addition of benzeneselenol and stirring at
room temperature to give the corresponding b-hydroxy
Cyclodextrins (CDs) are cyclic oligosaccharides possess-
ing hydrophobic cavities which bind substrates selec-
tively and catalyze chemical reactions with high
H
O
O
OH
β-CD/H2O
PhSeH/rt
R
SePh
R
Keywords: Oxiranes; Benzeneselenol; b-Hydroxy selenides; b-Cyclo-
dextrin; Supramolecular; Water.
R = aryloxy, aryl, hexyl
*
Corresponding author. Tel.: +91 4027193164; fax: +91
4027160512; e-mail: drkrrao@yahoo.com
Scheme 1.
0040-4039/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2005.10.094

8838
R. Sridhar et al. / Tetrahedron Letters 46 (2005) 8837–8839
Table 1. Oxirane opening with benzeneselenol in the presence of b-CD in water
Entry
1
Epoxide
Product
Time (min)
3
Yielda (%)
OH
O
O
O
SePh
0
0
0
5
5
86
86
84
82
82
O
OH
O
O
SePh
SePh
2
3
4
5
3
3
3
3
Cl
Cl
O
OH
O
O
H3C
H3C
MeO
O
OH
O
SePh
O
MeO
OH
O
O
SePh
O
MeO
MeO
MeO
MeO
SePh
6
7
3
5
80
O
OH
OH
OH
O
SePh
25
78
80
8
O
40
SePh
OH
9
O
40
40
80
75
SePh
OH
O
10
Cl
Cl
SePh
a Isolated yields after purification.
selenides in a highly regioselective fashion with impres-
sive yields (Table 1).9 This methodology is also
compatible with functionalities such as chloro, methyl,
methoxy and methoxyethyl. High selectivity was also
observed with styrene epoxide where the benzeneselenol
attacks the terminal carbon. These cyclodextrin-
mediated water-based reactions proceed under mild
conditions without generation of any toxic waste. b-
Cyclodextrin can also be easily recovered and reused.
The compounds were characterized by spectroscopy,
elemental analysis or otherwise compared with the
known compounds.6
The role of CD appears to be not only to activate the
oxiranes but also to promote highly regioselective ring
opening via inclusion complex formation. The complex
of epoxide and cyclodextrin, though generated in situ,
1
has been isolated and characterized by H NMR.10
There is an upfield shift of the H-3(0.03ppm) and
H-5 (0.057 ppm) protons of cyclodextrin in the CD–
epoxide complex as compared to CD indicating the
formation of an inclusion complex of the epoxide with
b-CD. In this type of complex, the a-position of the
epoxide is more hindered and b-attack predominates
to give a single regioisomer.
The reactions also take place with a-CD as well with the
same regioselectivity and stereochemistry, however, b-
CD was chosen as the catalyst since it is inexpensive
and easily accessible. These reactions do not proceed
in the absence of cyclodextrin. This is the first practical
regioselective ring opening of oxiranes with benzenesel-
enol in water. The reaction proceeds efficiently at room
temperature without the need of any acid, base and
metal catalyst. The reactions are also complete in a short
time (25–40 min).
These CD mediated water solvent reactions are very use-
ful both from economical and environmental points of
view in contrast to existing methodologies using di-
phenyldiselenide and metal catalysts. Thus, it has been
shown for the first time that b-hydroxy selenides of high
synthetic potential can be made in a biomimetic fashion
with high regioselectivity from easily accessible oxiranes
and benzeneselenol in the presence of b-cyclodextrin in
water. This methodology, which is simple and conve-
nient, should be a useful addition to modern synthetic

R. Sridhar et al. / Tetrahedron Letters 46 (2005) 8837–8839
8839
6. (a) Movassagh, B.; Shamsipoor, M. Synlett 2005, 1316–
1318; (b) Barros, O. S. do R.; de Carvalho, A. B.; Lang, E.
S.; Peppe, C. Lett. Org. Chem. 2004, 1, 43–46; (c) Labar,
D.; Krief, A. Tetrahedron Lett. 1978, 19, 3967–3970; (d)
Denis, J. N.; Vicens, J.; Krief, A. Tetrahedron Lett. 1979,
2697–2700; (e) Sharpless, K. B.; Lauer, R. F. J. Org.
Chem. 1974, 39, 429–430; (f) Nicolaou, K. C.; Claremon,
D. A.; Barnette, W. E.; Seitz, S. P. J. Am. Chem. Soc.
1979, 101, 3704–3706; (g) Cravador, A.; Krief, A. Tetra-
hedron Lett. 1981, 22, 2491–2494; (h) Engman, L.; Gupta,
V. J. Org. Chem. 1997, 62, 157–173; (i) Sakakibara, M.;
Katsumata, K.; Watanabe, Y.; Toru, T.; Ueno, Y.
Synthesis 1992, 377–379; (j) Dowsland, J.; McKerlie, F.;
Procter, D. J. Tetrahedron Lett. 2000, 41, 4923–4927; (k)
Nishiyama, Y.; Ohashi, H.; Itoh, K.; Sonoda, N. Chem.
Lett. 1998, 27, 159–160.
7. (a) Grieco, P. Organic Synthesis in Water; Blackie
Academic and Professional, 1998; (b) Li, C.-J. Chem.
Rev. 1993, 93, 2023–2035; (c) Lubineau, A.; Auge, J.;
Queneau, Y. Synthesis 1994, 741–760.
8. (a) Surendra, K.; Krishnaveni, N. S.; Rao, K. R. Synlett
2005, 506–510; (b) Krishnaveni, N. S.; Surendra, K.; Rao,
K. R. Chem. Commun. 2005, 669–671; (c) Krishnaveni,
N. S.; Surendra, K.; Rao, K. R. Adv. Synth. Catal. 2004,
346, 346–350; (d) Surendra, K.; Krishnaveni, N. S.;
Nageswar, Y. V. D.; Rao, K. R. J. Org. Chem. 2003, 68,
4994–4995.
9. General procedure: b-CD (1 mmol) was dissolved in water
(15 mL) under nitrogen by warming to 60 °C until a clear
solution was formed, then oxirane (1 mmol) dissolved in
acetone (1 mL) was added dropwise and the mixture was
allowed to reach room temperature. Benzeneselenol
(1.1 mmol) was then added and the mixture stirred at
room temperature until the reaction was complete (TLC)
(Table 1). The organic material was extracted with ethyl
acetate, dried and concentrated under reduced pressure.
The resulting crude product was further purified by silica
gel column chromatography with ethyl acetate–n-hexane
(2:8) as eluent.
10. (a) Surendra, K.; Krishnaveni, N. S.; Rao, K. R. Tetra-
hedron Lett. 2004, 45, 6523–6526; (b) Demarco, P. V.;
Thakkar, A. L. J. Chem. Soc., Chem. Commun. 1970, 2–3;
(c) Schneider, H.-J.; Hacket, F.; Rudiger, V. Chem. Rev.
1998, 98, 1755–1785.
methodology with the ever-growing demand for eco-
conscious chemical processes and increasing interest in
green chemistry.
Acknowledgement
K.S. and N.S.K. thank CSIR, New Delhi, India, for the
award of research fellowships.
References and notes
1. (a) Tiecco, M. In Topics in Current Chemistry; Wirth, T.,
Ed.; Springer: Berlin, 2000; pp 7–54; (b) Tomoda, S.;
Iwaoka, M. In Topics in Current Chemistry; Wirth, T.,
Ed.; Springer: Berlin, 2000; pp 55–80; (c) Tiecco, M.;
Testaferri, L.; Santi, C.; Tomassini, C.; Marini, F.;
Bagnoli, L.; Temperini, A. Angew. Chem., Int. Ed. 2003,
42, 3131–3133; (d) Krief, A. Tetrahedron 1980, 36, 2531–
2640; (e) Clive, D. L. J. Tetrahedron 1978, 1049–1132; (f)
Sharpless, K. B.; Yong, M. W.; Lauer, R. F. Tetrahedron
Lett. 1973, 14, 4923–4924.
2. (a) Sharpless, K. B.; Lauer, R. F. J. Am. Chem. Soc. 1973,
95, 2697–2699; (b) Hori, T.; Sharpless, K. B. J. Org. Chem.
1978, 43, 1689–1697; (c) Dumont, W.; Bayet, P.; Krief, A.
Angew. Chem., Int. Ed. Engl. 1974, 13, 804–806.
3. (a) Leonard-Coppens, A. M.; Krief, A. Tetrahedron Lett.
1976, 17, 3237–3240; (b) Remion, J.; Dumont, W.; Krief,
A. Tetrahedron Lett. 1976, 17, 1385–1388.
4. (a) Dumont, W.; Krief, A. Angew. Chem., Int. Ed. Engl.
1975, 14, 350–351; (b) Sevrin, M.; Dumont, W.; Hevesi,
L.; Krief, A. Tetrahedron Lett. 1976, 17, 2647–2650.
5. (a) Van Ende, D.; Dumount, W.; Krief, A. Angew. Chem.,
Int. Ed. 1975, 14, 700–702; (b) Van Ende, D.; Krief, A.
Tetrahedron Lett. 1976, 17, 457–460; (c) Gruttadauri, M.;
Aprile, C.; Riela, S.; Noto, R. Tetrahedron Lett. 2001, 42,
2213–2215; (d) Gruttadauri, M.; Lo Meo, P.; Noto, R.
Tetrahedron 2001, 57, 1819–1826; (e) Gruttadauri, M.; Lo
Meo, P.; Noto, R. Tetrahedron 1999, 55, 14097–14110; (f)
Gruttadauri, M.; Lo Meo, P.; Noto, R. Tetrahedron 1999,
55, 4769–4782; (g) Gruttadauri, M.; Noto, R. Tetrahedron
Lett. 1999, 40, 8477–8481.