M. Panunzio et al. / Tetrahedron: Asymmetry 13 (2002) 2113–2115
2115
briefly acidified to pH 3 with the addition of 10%
aqueous HCl, and subsequently basified (pH 8) by the
addition of solid NaHCO3. Acetone (2 mL) and ben-
zylchloroformate (0.11 mL, 3 mmol) were added to the
aqueous mixture. After 4 h, the reaction mixture was
extracted with ethyl acetate, washed with saturated
aqueous NaCl, dried (MgSO4), and concentrated in
vacuo. Flash chromatography on silica gel, eluting with
dichloromethane/acetone, 9/1, afforded 6 in 65%. Oil.
[h]2D0=−24.8 (c 0.87, CHCl3); IR: 3680, 3650, 1721,
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1
1686. H NMR: 7.35 (s, 5H); 6.45 (bs, 1H); 5.48 (d,
J=6.8, 1H); 5.12 (s, 2H); 4.86 (d, J=3.5, 1H); 4.36 (m,
1H); 4.06 (m, 3H); 1.14 (d, J=6.2, 1H); 1.04 (s, 21H).
13C NMR: 167.5; 156.2; 136.0; 128.5; 128.2; 84.5; 68.8;
68.2; 67.3; 50.7; 18.0; 17.9; 15.8; 12.1. MS m/z 450, 407,
363, 299, 273, 91. Elemental analysis found: C, 61.47;
H, 8.53; N, 6.20%. C23H38N2O5Si requires: C, 61.30; H,
8.50; N, 6.22%.
3.5. (2R)-Benzyloxycarbonylamino-3-hydroxy-propionic
acid methyl ester, 7
Compound 6 (0.1 mmol) was dissolved in MeOH (3
mL). The solution was cooled at 0°C, and 5 mL of a
previously prepared satured solution of HCl in MeOH
was added. After 2 h the solvent was removed in vacuo,
a saturated solution of NaHCO3 was added, and the
mixture was extracted with ethyl acetate. A simple
filtration on silica gel (CH2Cl2/acetone, 9/1) yielded the
target compound 7 in quantitative yield. Mp 31–33°C;
[h]2D0=+12.8 (c 0.9, CHCl3); 1H NMR: 7.35 (s, 5H);
5.72 (bs, 1H); 5.12 (s, 2H); 4.45 (m, 1H); 3.95 (m, 2H);
3.77 (s, 3H); 2.32 (bs, 1H). 13C NMR: 170.9; 156.2;
136.0; 128.6; 128.3; 128.1; 67.2; 63.3; 56.1; 52.7. MS
m/z 253, 162, 150, 108, 91. Elemental analysis found: C,
57.11; H, 5.99; N, 5.51%. C12H15NO5 requires: C, 56.91;
H, 5.97; N, 5.53%.
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