422
M. E. Gonzꢀalez-Rosende et al. / Tetrahedron: Asymmetry 15 (2004) 419–422
(3aR,4S,6aR)-4-Phenyltetrahydrofuro[3a-d][1,3]oxazol-
2(3H)-one 5. White solid. Mp 75–78 °C; ½a ¼ +79.7 (c
Acknowledgements
D
1.04, MeOH); IR (CH2Cl2) 1746 cmꢀ1
;
1H NMR
We are indebted to the Ministry of Science and Tech-
nology (ProjectPB98-1451) Spain, and MIUR, Iatly
(PRIN 2002) for financial support.
(CDCl3) d 3.04 (dd, J ¼ 5.1, J ¼ 2, 1H), 3.76 (d, J ¼ 2.0,
1H), 3.91 (m, 1H), 4.06 (dd, J ¼ 9.0, J ¼ 5.4, 1H), 4.45
(dd, J ¼ 9, J ¼ 8.6, 1H), 6.99 (br s, 1H), 7.14 (m, 2H),
7.22 (m, 3H); 13C NMR (CDCl3) d 53.1 (CH), 56.0
(CH), 62.3 (CH), 66.5 (CH2), 125.7 (CH), 128.5 (CH),
134.0 (CH), 135.5 (C), 160.0 (C@O); EI-HRMS calcd
for C11H11NO3 (M)þ 207.0738, found 207.0731.
References and notes
1. Walsh, H. A.; Leslie, P. L.; OÕShea, K. C.; Botting, N. P.
Bio. Med. Chem. Lett. 2002, 12, 361–363; Chiba, J.;
Yanaqawa, Y.; Masubuchi, Y.; Kataoka, H.; Kawaguchi,
T.; Ohtsuki, M.; Hoshino, Y. J. Inmunol. 1998, 160, 5037–
5044; Enders, D.; Haerting, A.; Runsink, J. Eur. J. Org.
Chem. 1998, 9, 1793–1802; Guarnieri, W.; Sendzik, M.;
(4R)-4-(2-Oxo-2-phenylethyl)-1,3-oxazolidin-2-one 6. To
a solution of 4b (1 g, 4.8 mmol) in acetone (12 mL)
cooled at0 °C was added dropwise freshly prepared 1 M
Jones reagent11 (4 mL, 5.3 mmol). After being stirred at
0 °C for 30 min, the reaction was quenched by addition
of isopropanol (9 mL) at the same temperature and
stirring was continued for another 30 min. The mixture
was decanted and the solution was concentrated to give
compound 6 (0.94 mg, 95%) as a white solid. Mp 134–
€
Frohlich, R.; Hoppe, D. Synthesis 1998, 1274–1286;
Gmeier, P.; Kartner, A. Synthesis 1995, 83–86; Kami-
mura, A.; Yoshihara, K.; Marumo, S.; Yamamoto, A.;
Nishiguchi, T.; Kakehi, A.; Kenzi, H. J. Org. Chem. 1992,
57, 5403–5413.
2. Garner, P.; Park, J. M. Org. Synth. Coll. Vol. IX 1998,
300; Dondoni, A.; Perrone, D. Synthesis 1997, 527–529;
Delle Monache, G.; Di Giovanni, M. C.; Maggio, F.;
Misiti, D.; Zappia, G. Synthesis 1995, 1155–1158; Meffre,
P.; Durand, P.; Branquet, E.; Le Goffic, F. Synth.
Commun. 1994, 24, 2147–2152.
1
137 °C; IR 3436, 1759, 1676 cmꢀ1; H NMR (CDCl3)
d 3.29 (m, 1H), 4.06 (dd, J ¼ 8.0, J ¼ 6.0, 1H), 4.35 (m,
1H), 4.60 (dd, J ¼ 8.8, J ¼ 8.4, 1H), 6.08 (br s, 1H), 7.41
(dd, J ¼ 8.3, J ¼ 7.3, 2H), 7.54 (tt, J ¼ 7.3, J ¼ 1.5, 1H)
7.86 (dd, J ¼ 8.3, J ¼ 1.5, 2H); 13C NMR (CDCl3) d 44.0
(CH2), 48.7 (CH), 70.0 (CH2), 128.0 (CH), 128.8 (CH),
134.0 (CH), 135.8 (C), 159.3 (C@O), 197.5 (C@O);
ꢀ
3. (a) Jorda-Gregori, J. M.; Gonzalez-Rosende, M. E.; Cava-
Montesinos, P.; Sepulveda-Arques, J.; Galeazzi, R.;
ꢀ
ꢀ
Orena, M. Tetrahedron: Asymmetry 2000, 11, 3769–3777;
ꢀ
(b) Jorda-Gregori, J. M.; Gonzalez-Rosende, M. E.;
Sepulveda-Arques, J.; Galeazzi, R.; Orena, M. Tetrahe-
½a ¼ 3.9 (c 1, MeOH); EI-HRMS calcd for C11H11NO3
D
ꢀ
(Mþ) 205.0738, found 205.0731.
ꢀ
dron: Asymmetry 1999, 10, 1135–1143.
4. Delle Monache, G.; Misiti, D.; Zappia, G. Tetrahedron:
Asymmetry 1999, 10, 2961–2973; Avenoza, A.; Cativiela,
ꢀ
4.3. Preparation of amino diol derivatives 1a and 1b.
General procedure
C.; Fernadez-Recio, M. A.; Peregrina, J. M. Tetrahedron:
Asymmetry 1996, 7, 721–728; Guindon, Y.; Slassi, A.;
Rancourt, J.; Bantle, G.; Bencheqroun, M.; Murtagh, L.;
Ghiro, E.; Jung, G. J. Org. Chem. 1995, 60, 288–289;
Bongini, A.; Cardillo, G.; Orena, M.; Porzi, G.; Sandri, S.
Tetrahedron 1987, 43, 4377–4383; Kamiyana, K.; Urano,
Y.; Kobayashi, S.; Ohno, M. Tetrahedron Lett. 1987, 28,
3123–3126; Hirama, M.; Iwashita, M.; Yamakazi, Y.; Ito,
S. Tetrahedron Lett. 1984, 25, 4963–4964; Georges, M.;
Fraser-Reid, B. Tetrahedron Lett. 1981, 22, 4635–4638;
Kuivila, H. G. Synthesis 1970, 499.
To a solution containing oxazinone 3a or oxazolidinone
4b (10 mmol) in ethanol (25 mL) was added a 5 M
solution of NaOH (25 mL) and the mixture was refluxed
for 5 h. When the reaction was completed 5% HCl was
added. The reaction was then extracted with ethyl ace-
tate and dichloromethane. The combined organic layers
were dried over Na2SO4, filtered and concentrated under
reduced pressure. The residue was purified by flash
column chromatography (hexane, ethyl acetate and
methanol with gradient polarity).
5. Compound 4a is thought to come from the reduction of
iodine and further attack of the intermediate tin alkoxide
onto the oxazinone carbamate. The reaction was unex-
pected, as it has been reported hydroxyl groups need not
to be protected under conditions where radicals are
generated. Paquette, L. A. In Encyclopedia of Reagents
for Organic Synthesis; John Wiley: 1995; p 5017.
6. Agami, C.; Couty, F. Tetrahedron 2002, 58, 2701–2724.
7. Williams, A. L.; Abad Grillo, T.; Comins, D. L. J. Org.
Chem. 2002, 67, 1972–1973.
(2R,4S)-2-Amino-pentane-1,4-diol 1a. Yield 0.85 g,
71%; ½a ¼ +10.7 (c 1.02, MeOH); 1H NMR (D2O)
D
d 1.05 (d, J ¼ 6.2, 3H), 1.40–1.55 (m, 2H), 3.24 (m, 1H),
3.37 (dd, J ¼ 7.35, J ¼ 12.4, 1H), 3.59 (m, 1H), 3.77 (m,
1H); 13C NMR (D2O) d 22.7 (CH3), 37.2 (CH2), 50.9
(CH), 61.8 (CH2), 64.4 (CH), 156.1 (C@O); EI-
HRMS calcd for C5H14NO2 (MH)þ 120.1024, found
120.1016.
8. Foglia, T. W.; Swern, D. J. Org. Chem. 1969, 34, 1680–
1684.
9. Parker, K. A.; OÕFee, R. J. Am. Chem. Soc. 1983, 105,
654–655.
10. Kemp, S. J.; Bao, J.; Pedersen, F. J. Org. Chem. 1996, 61,
7162–7167.
(1S,3R)-3-Amino-1-phenylbutane-1,4-diol 1b. Yield
1.17 g, 65%; ½a ¼ )3.46 (c 1.04, MeOH); 1H NMR
D
11. Mc Killop, A.; Taylor, R. J. K.; Watson, R. J.; Lewis, N.
Synthesis 1994, 31–34; Moriwake, T.; Hamano, S. I.;
Saito, S.; Torii, S. Chem. Lett. 1987, 2085–2088.
12. Sugimura, M.; Miura, M.; Yamada, N. Tetrahedron:
Asymmetry 1997, 8, 4089–4099.
(CDCl3) d 1.9–2.2 (m, 5H), 3.7 (dd, J ¼ 8.85, J ¼ 3.75,
2H), 3.8 (m, 1H), 4.1 (dd, J ¼ 8.85, J ¼ 5.3, 1H), 5.2 (dd,
J ¼ 8.6, J ¼ 6.6, 1H); 13C NMR (CDCl3) d 44.8 (CH2),
52.8 (CH), 64.0 (CH2), 79.9 (CH), 126.0 (CH), 127.7
(CH), 128.8 (CH), 143.1 (C); EI-HRMS calcd for
C10H15NO2 (M)þ 181.1102, found 181.1094.
ꢀ
13. Jaouen, V.; Jegou, A.; Verieres, A. Synlett 1996, 1218–
ꢁ
1220.