Compound 17b was also prepared from 2-azido-D-talono-1,4-
lactone 15 as described for the enantiomer ent-17: mp 155 ◦C;
[a]2D0 EQ/S −9.48 (c 1.1, H2O); found; C, 36.91; H, 6.67; N, 7.06;
was dissolved in MeOH (3 mL) and cooled to 0 ◦C. Et3N (0.6 mL,
4.23 mmol) was added at 0 ◦C and stirring was continued overnight
at rt. Concentration gave a light yellow crude product, which
was dissolved in H2O (5 mL) and poured onto a column of ion-
exchange resin. The column was eluted with aq. NH3 (6%, 80 mL,
12.5%, 60 mL) and the eluate concentrated to give crystalline ent-
17 (0.19 g, 75%). Recrystallisation from H2O–EtOH afforded an
analytical sample of ent-17 (79 mg, 32% yield): mp 208–210 ◦C
(decomp.); [a]2D0 +10.3 (c 0.57, H2O); found: C, 36.96; H, 6.63;
N, 7.11; Calc. for C6H11O5N·H2O; C, 36.92; H, 6.71, N, 7.18; 1H
NMR (500 MHz, D2O, pH 7): dH 3.21 (1H, dd, J = 12.8, 7.7 Hz,
H-1), 3.40 (1H, dd, J = 12.8, 3.8 Hz, H-1ꢀ), 3.76 (1H, dd, J = 7.3,
2.4 Hz, H-3), 3.94 (1H, d, J = 6.0 Hz, H-5), 4.10 (1H, ddd, J =
7.7, 7.3, 3.8 Hz, H-2), 4.39 (1H, dd, J = 6.0, 2.4 Hz, H-4); 13C
NMR (75 MHz, D2O, pH 7): dC 44.6 (C-1), 60.1 (C-5), 65.5, 68.0,
70.4 (C-2, C-3, C-4), 171.4 (C-6).
1
Calc. for C6H11O5N,H2O; C, 36.92; H, 6.71, N, 7.18; H NMR
(500 MHz, D2O): dH 3.16 (1H, dd, J = 13.2, 7.7 Hz, H-1), 3.36
(1H, dd, J = 13.2, 3.8 Hz, H-1ꢀ), 3.71 (1H, dd, J = 7.3, 2.6 Hz,
H-3), 3.89 (1H, d, J = 6.4 Hz, H-5), 4.05 (1H, ddd, J = 7.7,
7.3, 3.8 Hz, H-2), 4.34 (1H, dd, J = 6.4, 2.6 Hz, H-4); 13C NMR
(75 MHz, D2O): dC 44.8 (C-6), 60.3 (C-2), 65.7, 68.2, 70.6 (C-3,
C-4, C-5), 171.6 (C-1).
2-Azido-6-bromo-2,6-dideoxy-L-galactono-1,4-lactone (ent-12)
and -L-talono-1,4-lactone (ent-13)
2,6-Dibromo-2,6-dideoxy-L-galactono-1,4-lactone
(ent-11)18
(3.12 g, 10.27 mmol) and NaN3 (9.3 g, 3 w%) in dry acetone
(60 mL, MgSO4) were stirred vigorously under reflux for 17 h.
Work-up as described for the enantiomers 12 and 13 gave a
semicrystalline product in quantitative yield (ent-12 and ent-13
in the ratio 1 : 1.2 according to 13C NMR). Crystallisation from
5 mL EtOAc afforded 0.49 g of ent-13 as colourless crystals. Flash
chromatography (EtOAc–pentane 1 : 2) of the residue gave: ent-12
(1.27 g, 47%, Rf = 0.28) and ent-13 (0.36 g, Rf = 0.18, total 31%).
Overall yield 78%. ent-12: mp 110–112 ◦C; found; C, 27.36; H,
2.87; N, 15.58; Br, 29.94; Calc. for C6H8BrO4N3; C, 27.09; H, 3.03;
N, 15.79; Br, 30.03; NMR data were identical with those reported
for the enantiomer: 13C NMR (62.5 MHz, acetone-d6): dC 33.5
Acknowledgements
T.M.W. thanks the Department of Organic Chemistry at DTU,
Lyngby, and Prof. Inge Lundt’s group for a scientifically inspiring
sabbatical stay.
References and notes
1 (a) P. Compain and O. R. Martin, Iminosugars: From Synthesis to
Therapeutic Applications, Wiley & Sons, Chichester, 2007; (b) A. E.
Stu¨tz, Iminosugars as Glycosidase Inhibitors, Wiley-VCH, Weinheim,
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=
(C-6), 65.2 (C-2), 69.1, 72.5 (C-3, C-5), 81.7 (C-4), 170.9 (C O).
ent-13: mp 153–155 ◦C; NMR data were identical with those
reported for the enantiomer: 13C NMR (62.5 MHz, acetone-d6):
dC 33.2 (C-6), 61.2 (C-2), 71.6, 72.6 (C-3, C-5), 86.7 (C-4), 172.7
=
(C O).
(2S,3S,4R,5S)-3,4,5-Trihydroxypipecolic acid
(2,6-dideoxy-2,6-imino-L-galactonic acid) (ent-16)
2-Azido-6-bromo-L-galactono-1,4-lactone (ent-12) (0.53 g,
1.97 mmol) was hydrogenated in MeOH (10 mL) in the presence
of 50 mg Pd/C (5%) and 0.5 mL conc. HCl at 1 atm for 16 h.
The catalyst was filtered off and the filtrate was concentrated
and co-evaporated with conc. HCl and toluene (3 × 5 mL)
to give the hydrochloride salt of ent-14 in quantitative yield.
2-Amino-L-galacto-1,4-lactone ent-14 (0.78 g, 2.82 mmol) was
treated with KOH and worked up as described above for the
enantiomer to give ent-16 (0.33 g, 66%) after crystallisation; mp
270 ◦C (decomp.); [a]D20 EQ/S +18.7 (c 1.0, H2O); found; C, 37.03;
H, 6.71; N, 7.08; Calc. for C6H11O5N,H2O; C, 36.92; H, 6.71;
N, 7.18; (FAB+): m/z 178.0717 (M + H+) (C6H12O5N requires
178.0715); NMR data were identical with those reported for
the enantiomer 16. The compound has been reported,14 but no
spectral and analytical data were given.
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(2R,3S,4R,5S)-3,4,5-Trihydroxypipecolic acid
(2,6-dideoxy-2,6-imino-L-talonic acid) (ent-17)
2-Azido-6-bromo-L-talonolactone ent-13 (0.38 g, 1.41 mmol) was
hydrogenated in MeOH (8 mL) in the presence of 40 mg Pd/C (5%)
and 0.8 mL conc. HCl at 1 atm for 16 h. The catalyst was filtered
off and the filtrate was concentrated and co-evaporated with conc.
HCl and toluene (3 × 5 mL) to give the hydrochloride salt of ent-
15 in quantitative yield. The 2-amino-L-talo-1,4-lactone ent-15
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