E. J. Alvarez-Manzaneda et al. / Tetrahedron Letters 45 (2004) 4453–4455
4455
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5th ed.; Wiley Interscience: New York, 2001, pp 1326–1328;
(d) Larock, R. C. Comprehensive Organic Transformations;
VCH, 1989. pp 151–154.
Experimental procedure: Iodine (1.2 mmol) was added to
a solution of Ph3P (1.2 mmol) in CH2Cl2 (5 mL) and the
mixture was stirred at room temperature for 10 min. A
solution of the alcohol (1.0 mmol) in CH2Cl2 (3 mL) was
then added and the mixture was further stirred at room
temperature, the reaction being monitored by TLC. Aq
5% NaHSO3 was added and the mixture was stirred for
10 min. It was then diluted with CH2Cl2 and the organic
phase washed with H2O and brine successively, after
which it was dried and evaporated to give a crude. This,
after flash column chromatography on silicagel (hexane/
ether), gave the alkene.
2. (a) Fieser, L. F.; Fieser, M. In Reagents for Organic
Synthesis; John Wiley: New York, 1967; Vol. I, pp 498–504;
(b) Reeve, W.; Reichel, D. M. J. Org. Chem. 1972, 37, 68–
72; (c) Elsner, B. B.; Strauss, H. E. J. Chem. Soc. 1957, 288–
292; (d) Hibbert, H. J. Am. Chem. Soc. 1915, 37, 1748–
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3. Theil, F.; Linding, C.; Repke, K. Zeitschrift fuer Chemie
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1994, 35, 5035–5038.
5. (a) Barrero, A. F.; Alvarez-Manzaneda, E.; Chahboun, R.;
Meneses, R. Synlett 1999, 1663–1666; (b) Barrero, A. F.;
Alvarez-Manzaneda, E.; Chahboun, R.; Meneses, R. Syn-
lett 2000, 197–200; (c) Barrero, A. F.; Alvarez-Manzaneda,
E.; Chahboun, R. Tetrahedron Lett. 2000, 41, 1959–1962;
(d) Barrero, A. F.; Alvarez-Manzaneda, E.; Chahboun, R.;
Cuerva, J. M.; Segovia, A. Synlett 2000, 1269–1272; (e)
Barrero, A. F.; Alvarez-Manzaneda, E.; Chahboun, R.;
Meneses, R.; Romera, J. L. Synlett 2001, 485–488.
6. Corey’s iodination procedure involves the transformation
of primary and secondary alcohols into the corresponding
iodides by treatment with a mixture of triphenylphosphine–
iodine–imidazole in acetonitrile–ether; Corey, E. J.; Pyne,
S. G.; Su, W. Tetrahedron Lett. 1983, 24, 4883–4886, The
tertiary hydroxy groups remained unaltered under these
conditions.
In conclusion, the Ph3P–iodine system is an inexpensive
reagent, which transforms tertiary alcohols into the
most stable alkene, under mild and easily-implemented
experimental conditions. Some functional groups, such
as ketone, ester and amide, remain unaltered under these
conditions.
Acknowledgements
Financial support was received from Ministerio de
Ciencia y Tecnologia (Project PPQ 2002-03308).
7. Hagiwara, H.; Takeuchi, F.; Hoshi, T.; Suzuki, T.; Ando,
M. Tetrahedron Lett. 2001, 42, 7629–7631.
References and notes
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