S. J. Katz, S. C. Bergmeier / Tetrahedron Letters 43 (2002) 557–559
559
ported ethylenediamine. While such a reagent would
produce a similar cyclic urea, it could be readily
removed by filtration.
12. Bergmeier, S. C.; Stanchina, D. M. J. Org. Chem. 1997,
62, 4449–4456.
13. DiGiovanni, M. C.; Misiti, D.; Villani, C.; Zappia, G.
Tetrahedron: Asymmetry 1996, 8, 2277–2286.
Treatment of oxazolidinone 3h with polymer supported
ethylenediamine20 at 60°C did provide the aminoalco-
hol 4h. However a small amount of 12 (6%) was also
produced. By first washing the resin exhaustively with
THF any free ethylenediamine was removed and the
reaction gave clean aminoalcohol 4h in 98% yield after
filtration and concentration (Table 1, entry 9). We then
tested the resin on a variety of oxazolidinones to test its
versatility.
14. Burk, M. J.; Allen, J. G. J. Org. Chem. 1997, 62, 7054–
7057.
15. Flynn, D. L.; Zelle, R. E.; Grieco, P. A. J. Org. Chem.
1983, 48, 2424–2426.
16. Seebach, D.; Fadel, A. Helv. Chim. Acta 1985, 68, 1243–
1250.
17. Aldrich Technical Bulletin AL-142.
18. 1H NMR of all known aminoalcohols were compared to
literature data. 1H NMR spectra of aminoalcohols 4e and
4f are provided below: 4e: 1.0 (s, 1H), 1.2 (m, 7H), 1.6 (t,
J=5.25 Hz, 2H), 1.8 (dd, J=4, 7.75 Hz, 2H), 2.2 (d,
J=8.25 Hz, 2H), 2.6 (d, J=10.75 Hz, 2H), 7.6 (m, 5H),
7.8 (m, 15H); 4f: 1.0 (s, 1H), 1.2 (m, 7H), 1.6 (t, J=5.25
Hz, 2H), 1.8 (dd, J=4, 7.75 Hz, 2H), 2.2 (d, J=8.25 Hz,
2H), 2.6 (d, J=10.75 Hz, 2H), 7.6 (m, 5H).
As before we chose a variety of substituted oxazolidi-
nones. We examined the effect of substitution at the 4-,
5-, as well as both the 4- and 5-positions (Table 1,
entries 9–13). In all cases the yields were >90%.
Through the use of a solid supported base we have
developed a convenient method for hydrolysis of oxa-
zolidinones that minimizes clean up and reduces the
extreme conditions previously needed. Using Dowex
1×8-100 resin as our supported base, we were able to
hydrolyze a variety of N-substituted oxazolidinones as
well as an oxazenone and a phenyl carbamate. By using
resin bound ethylenediamine we were able to hydrolyze
various N-unsubstituted oxazolidinones. Together these
methods provide a more efficient method for the
hydrolysis of oxazolidinones.
19. The oxazolidinone was dissolved in MeOH:THF (3:1, 0.3
M) and Dowex 1×8-100 resin (350 mol% of the hydroxide
form, as purchased the resin was in the chloride form and
was washed with 200 mL of 3 M NaOH, 100 mL of H2O,
50 mL of MeOH, and dried overnight under vacuum)
was added. The suspension was stirred at rt until com-
plete by TLC (18–24 h), filtered, washed with EtOAc, and
concentrated to yield the product.
20. N-(2-Aminoethyl)aminomethyl polystyrene (300 mol%,
1% DVB, 1.3 mmol/g from Novabiochem) was washed
with THF (3×25 mL) and added to a solution of the
oxazolidinone (100 mol%) in THF (0.3 M). The suspen-
sion was warmed to 60°C and stirred until complete
(18–24 h). The reaction was filtered, washed with EtOAc,
and concentrated to provided the desired amino alcohol.
21. Kubota, Y.; Kodaka, M.; Tomohiro, T.; Okuno, H. J.
Chem. Soc., Perkin Trans. 1 1993, 5–6.
Acknowledgements
We would like to thank the Office of the Vice-President
for Research at Ohio University for support of this
research through a Research Challenge Grant.
22. Prepared by the reaction of 4-methyl-5-phenyl-2-oxazo-
lidinone and (1-bromoethyl)benzene with KF/Al2O3.23
23. Blass, B. E.; Drowns, M.; Harris, C.; Liu, S.; Portlock,
D. Tetrahedron Lett. 1999, 40, 6545–6547.
References
24. Prepared by the reaction of 4-methyl-5-phenyl-2-oxazo-
lidinone and the corresponding aryl bromide with
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28. Wuts, P.; Pruitt, L. Synthesis 1989, 622–623.
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30. The four Dowex resins tried were: 1×8-100 (microporous,
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porous, dimethyl-2-hydroxyethylbenzyl ammonium).
31. Perrin, D. D. Dissociation Constants of Organic Bases;
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