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acid (2 M, 2 mL) was then added to the reaction mixture which was
then stirred for a further 16 h under hydrogen. The catalyst was
then removed by filtration through a short pad of CeliteÒ and the
filtrate concentrated to approx 2 mL under reduced pressure. The
concentrate was then loaded onto a column of DowexÒ 50W-X8
(H+ form), washed with water, and the amino acid 5L liberated
with 2 M aqueous ammonia. The ammoniacal fractions were com-
bined and concentrated under reduced pressure to give the sugar
amino acid 5L (119 mg, 77%) as pale yellow gum, which crystal-
lized on standing, mp 176 °C (decomp); ½a D25
¼ þ14:7 (c 1.1,
ꢁ
H2O); HRMS (ESI +ve); C6H11NNaO5 found 200.0526; (M+Na+) re-
quires 200.0529; mmax (thin film, Ge): 3356 (s, NH/OH), 1634 (s,
CO); dH (D2O, 400 MHz): 3.69 (1H, a-dt, H5 J5,6a 6.8, J5,6b, J5,4 5.1),
3.84 (1H, dd, H6a Jgem 12.4, J6a,5 6.8), 3.92 (1H, dd, H6b Jgem 12.4,
J6a,5 4.5), 3.95 (1H, d, H2 J2,3 4.3), 4.06 (1H, dd, H4 J4,3 4.5, J4,5
5.3), 4.34 (1H, t, H3 J3,2, J3,4 4.5); dC (D2O, 100 MHz): 59.3 (C6),
65.3 (C5), 66.0 (C2), 76.2 (C4), 79.0 (C3), 173.0 (C1); LRMS (ESI
ꢀve): 176 (69%, [MꢀH]ꢀ), 353 (100%, [2MꢀH]ꢀ).
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4.4.2. (2R,3S,4S,5S)-3,4-Dihydroxy-5-(hydroxymethyl)-
D-proline
[(3S)-3-hydroxy- -bulgecinine] 5D
D
The same sequence of reactions on the enantiomeric azido lac-
tone 17L (1.00 g, 2.61 mmol) gave the enantiomeric amino acid 5D
(396 mg, 2.25 mmol), mp 174 °C (decomp), ½a D25
ꢁ
¼ ꢀ15:1 (c 1.0,
H2O), in 86% yield from 5-azido-3,6-di-O-benzyl-5-deoxy-
L
-gluc-
ono-1,4-lactone (1.00 g, 2.61 mmol). Other spectroscopic data of
5D were identical to those of its enantiomer 5L.
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