M. D. Milton et al. / Tetrahedron Letters 46 (2005) 755–758
757
(HOCH2SO2NaÆ2H2O), elemental selenium and 2-chloro-
ethanol at room temperature for 5 h and yields only 39%
of HOCH2CH2Se–SeCH2CH2OH after distillation. Fol-
lowing this procedure, we observed the formation of both
1 and 9; extraction and purification of the product from
the resulting mixture proved to be a long and tedious
procedure. During distillation of the final product, exten-
sive decomposition was observed and the product, in our
hands, was obtained in a yield of 25–32%; (b) Sang, I. K.;
Spears, C. P. Synthesis 1988, 133–135, this method
involves reaction of 2-bromoethanol with potassium
selenocyanate in boiling acetone to give 2-hydroxyethylse-
lenocyanate in 80% yield. The selenocyanate was con-
verted in situ in the presence of sodium borohydride to the
corresponding selenolate anions which react with electro-
philic substrate; (c) Back, T. G.; Moussa, Z. J. Am. Chem.
Soc. 2003, 125, 13455–13460, this article deals with a series
of aliphatic diselenides and selenides containing coordi-
nating substituents which were tested for glutathione
peroxidase (GPx)-like catalytic activity in a model system
in which the reduction of tert-butyl hydroperoxide with
benzyl thiol to afford dibenzyl disulfide and tert-butyl
alcohol was performed under standard conditions. In
particular, allyl 3-hydroxypropyl selenide rapidly gener-
ated 1,2-oxaselenolane Se-oxide in situ by a series of
oxidation and [2,3]sigmatropic rearrangement steps.
8. (a) Gladysz, J. A.; Hornby, J. L.; Garbe, J. E. J. Org.
Chem. 1978, 43, 1204–1208; (b) Yamahira, A.; Nogami,
T.; Mikawa, H. J. Chem. Soc., Chem. Commun. 1983, 904–
905; (c) Krief, A.; Derock, M. Tetrahedron 2002, 43, 3083–
3086.
addressing these issues is already underway in our labo-
ratories together with the development of synthetic
routes for chalcogen-containing macrocycles, azacrown
and crown ethers using these species as source precur-
sors, and will be reported in due course.
Acknowledgements
This research was supported by the Department of
Science and Technology (DST), Government of India
(Grant SP/S1/F-18/1998). We are also thankful to the
UGC and CSIR for providing research fellowships to
(M.D.M.) and (S.K.). Thanks are also due to RSIC,
Lucknow, India, for providing ES-MS spectra. We are
thankful to the reviewer, with gratitude, for his valuable
comments and suggestions to improve this manuscript
greatly.
References and notes
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da Cruz, M. T.; Pedroso de Lima, M. C.; Pereira, E.;
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47, 2917–2925.
2. (a) Milton, M. D.; Kumar, N.; Sokhi, S. S.; Singh, S.;
Singh, J. D. Tetrahedron Lett. 2004, 45, 6453–6455; (b)
Milton, M. D.; Singh, J. D.; Butcher, R. J. Tetrahedron
Lett. 2004, 45, 6745–6747; (c) Kumar, N.; Milton, M. D.;
Singh, J. D. Tetrahedron Lett. 2004, 45, 6611–6613; (d)
Milton, M. D.; Singh, J. D.; Khandelwal, B. L.; Kumar,
P.; Singh, T. P.; Butcher, R. J. Phosphorus, Sulfur, Silicon
2001, 172, 231–238.
3. (a) Wirth, T. Tetrahedron 1999, 55, 1–28; (b) Wirth, T.
Angew. Chem., Int. Ed. 2000, 39, 3740–3749; (c) Topics in
Current Chemistry: Organoselenium Chemistry, Modern
Developments in Organic Synthesis; Wirth, T., Ed.;
Springer: Berlin, Germany, 2000.
4. (a) Clive, D. L. J. Tetrahedron 1978, 34, 1049–1132; (b)
Krief, A. Tetrahedron 1980, 36, 2531–2640; (c) These two
excellent reviews cover the synthesis of b-, c- and d-
hydroxyalkylselenides generated in situ by normal SN2
opening of the ring by PhSeꢁNa+ or PhSeH and their
utility in organic transformations.
5. (a) Aprile, C.; Gruttadauria, M.; Amato, M. E.; Noto;
DꢀAnna, F.; Lo Meo, P.; Riela, S.; Noto, R. Tetrahedron
2003, 59, 2241–2251; (b) Gruttadauria, M.; Aprile, C.;
DꢀAnna, F.; Lo Meo, P.; Riela, S.; Noto, R. Tetrahedron
2001, 57, 6815–6822; (c) These two articles cover the
stereoselective synthesis of oxygenated heterocyclic rings
from mixtures of hydroxy selenides.
6. (a) Tanaka, H.; Sakurai, H.; Yokoyama, A. Chem. Pharm.
Bull. 1970, 18, 1015–1019; (b) Yarovenko, N. N.; Raksha,
M. A.; Shemanina, V. A. J. Org. Chem. USSR (Engl
Trans.) 1960, 4032–4035, this communication deals with
2-hydroxyethylseleno compounds; 2-hydroxyethylselenol
HOCH2CH2SeH and its corresponding diselenide
HOCH2CH2Se–SeCH2CH2OH. This procedure is based
on the reaction of ethylene oxide and hydrogen selenide in
a sealed ampoule at room temperature and under pressure
for 100 h and gave only 38% of HOCH2CH2SeH and 12%
of HOCH2CH2Se–SeCH2CH2OH as a mixture.
9. (a) Klayman, D. L.; Griffin, T. J. Am. Chem. Soc. 1973,
95, 197–199; (b) Tellurium in Organic Synthesis; Petrag-
nani, N.; Academic Press Limited: London, 1994, John
Wiley and Sons, New York, 1973.
10. In a representative reaction, sodium selenide was gener-
ated by reaction of gray elemental selenium (0.79 g,
10 mmol) and sodium hydroxide (0.88 g, 22 mmol) and
NaBH4 (0.84 g, 22 mmol) (exothermic) in aqueous THF
(20 mL + 0.2 mL H2O) under N2. The colorless sodium
selenide solution thus obtained was was allowed to warm
to room temperature over 0.5 h then treated with a
solution of 3-chloropropanol (1.89 g, 20 mmol) in THF
(10 mL) under N2. The reaction mixture was stirred
overnight at room temperature, and concentrated under
reduced pressure. The residual mass was diluted with
deionized water and extracted with chloroform
(3 · 25 mL). The combined organic fractions were col-
lected, dried over magnesium sulfate, filtered, and the
solvent was removed in vacuo yielding a nearly colorless,
viscous liquid that was found to be essentially free from
diselenide derivatives. In rare cases, where formation of a
slight amount of diselenide was observed, it was simply
removed by column chromatography (CHCl3:CH3OH
95:5) on silica gel to afford pure bis(hydroxyalkyl)selenide.
Bis(hydroxy)tellurides were also prepared similarly from
Na2Te [generated in an identical way except that the
reaction mixture in the case of tellurium was warmed for a
short time (55–65 ꢁC) to complete the dissolution of the
tellurium (ca. 20 min)] and the corresponding bromo
compounds. Satisfactory analyses and spectral data were
1
obtained for all new compounds. H NMR data of some
representative compounds are reported as follows:
[HO(CH2)2Se(CH2)2OH] 1: colorless viscous liquid; NMR
(CDCl3): 1H (300 MHz),
d
3.92 (t, 4H, J(HH)
7 Hz, –OCH2), 3.1 (t, 4H, J(HH) 6 Hz, –SeCH2), 2.35
(s, 2H, OH); 13C (75 MHz), d 61.72 (OCH2), 20.04 (Se–
CH2). [HO(CH2)3Se(CH2)3OH] 2: colorless viscous liquid;
NMR (CDCl3): 1H (300 MHz), d 3.73 (t, 4H, J(HH) 7 Hz,
7. (a) Lingren, B. Acta Chem. Scand. Ser. B 1977, 31, 1–6,
this method uses sodium formaldehydesulfoxylate