M. S. Reddy et al. / Tetrahedron 63 (2007) 331–336
335
0.025 mmol) and the reaction mixture was allowed to stir
Acknowledgements
under an H2 atmosphere for 1 h. The reaction mixture was
filtered through Celite and evaporated to dryness under
reduced pressure. The crude residue was purified by column
chromatography (SiO2, 6% EtOAc in petroleum ether
eluent) to afford 16 (120 mg, 98%) as a light yellow liquid.
M.S.R. and M.N. thank CSIR, New Delhi, India for the
award of research fellowships.
[a]2D5 ꢂ34.8 (c 0.56, CHCl3); IR (KBr): nmax 3446.0, 2932.8,
References and notes
1
1694.5, 1419.8, 1153.9, 1041.8 cmꢂ1; H NMR (CDCl3,
300 MHz) d 4.65 (d, 1H, J¼6.8 Hz, OCHAHBO), 4.59 (d,
1H, J¼6.8 Hz, OCHAHBO), 3.92–3.45 (m, 3H, CHOCH2,
H2, H6), 3.35 (s, 3H, OMe), 3.12–2.91 (m, 2H, H2, H6),
1.98–1.83 (m, 1H, H4), 1.82–1.65 (m, 1H, H5), 1.58–1.21
1. (a) Von Itzstein, M.; Wu, W.-Y.; Kok, G. B.; Pegg, M. S.;
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t
(m, 11H, including s for Bu, H4, H5); 13C NMR (CDCl3,
50 MHz): d 154.9, 94.7, 79.5, 76.4, 70.9, 55.2, 47.7, 30.7,
28.3, 22.6; MS (ESIMS): m/z 246 [M+H]+; HRMS (ESI)
calcd for C12H24NO4 [M+H]+: 246.1714, found: 246.1705.
4.1.12. (3R,5R)-Piperidine-3,4,5-triol hydrochloride (1).
To a solution of 15 (100 mg, 0.36 mmol) in distilled
MeOH (2 mL) was added 6 M HCl (0.04 mL) and the reac-
tion mixture was allowed to warm to room temperature and
was stirred overnight. The reaction mixture was passed
through a short pad of Celite and the solvent was removed
under reduced pressure to afford 1$HCl (43 mg, 90%) as
a white solid.
Mp¼190–191 ꢀC; [a]2D5 ꢂ15.0 (c 0.42, MeOH) (lit.9a,d mp
191–192 ꢀC, [a]D20 ꢂ16.0 (c 0.9, MeOH)); IR (neat): nmax
3388.4, 3070.5, 2925.3, 1465.4, 1082.2 cmꢂ1 1H NMR
;
(D2O, 200 MHz) d 4.23–4.18 (m, 1H, H5), 4.12–4.01 (m,
1H, H3), 3.73 (dd, 1H, J¼7.5, 2.7 Hz, H4), 3.36 (dd, 1H,
J¼12.3, 4.1 Hz, H2eq), 3.32–3.12 (m, 2H, H6eq, H6ax), 2.92
(dd, 1H, J¼12.3, 8.2 Hz, H2ax); 13C NMR (D2O, 75 MHz):
d 70.9, 65.2, 64.8, 46.3, 45.6; MS (ESIMS): m/z 134
[M+H]+; HRMS (ESI) calcd for C5H12NO3 [M+H]+:
134.0821, found: 134.0817.
4.1.13. (S)-tert-Butyl 3-hydoxy piperidine-1-carboxylate
(4). A solution of piperidine 16 (100 mg, 0.4 mmol) in dis-
tilled MeOH (2 mL) was treated with 6 M HCl (0.04 mL)
and stirred at room temperature for 7 h. The reaction mixture
was evaporated under reduced pressure. The resulting resi-
due was dissolved in MeOH (4 mL) and Et3N (0.11 mL,
2 mmol) and Boc2O (0.11 mL, 0.48 mmol) were added
successively and the reaction mixture was stirred at room
temperature for 30 min. Then the solvent was removed
under reduced pressure and the residue was diluted with wa-
ter and extracted with ethyl acetate (3ꢁ15 mL). The organic
phase was dried over anhydrous sodium sulfate and concen-
trated in vacuo. The residue thus obtained was purified by
column chromatography (SiO2, 25% ethyl acetate/hexane
eluent) to afford 4 (72 mg, 89%) as a colorless liquid.
[a]2D5 +23.0 (c 0.65, EtOH) (lit.18c,9d [a]2D5 +23.5 (c 1.46,
EtOH)); IR (neat): nmax 3424.8, 2928.6, 2857.9, 1693.8,
1426.0 cmꢂ1 1H NMR (CDCl3, 300 MHz) d 3.77–3.63
;
(m, 2H, H2, H6), 3.56–3.39 (m, 1H, CHOH), 3.23–2.99
(m, 2H, H2, H6), 1.91–1.66 (m, 2H, H4, H5), 1.59–1.33 (m,
t
11H, including s for Bu, H4, H5); 13C NMR (CDCl3,
75 MHz): d 157.7, 77.8, 72.5, 51.5, 42.8, 33.3, 29.2, 22.5;
MS (ESIMS): m/z 202 [M+H]+; HRMS (ESI) calcd for
C10H20NO3 [M+H]+: 202.1452, found: 202.1443.