2452
J. Jeon et al. / Tetrahedron: Asymmetry 18 (2007) 2448–2453
HRMS (CI) calcd for C29H32NO5 [M+H]+: 474.2280;
found, 474.2280.
5.0 mmol) at 0 ꢁC. Then, the reaction mixture was heated
at reflux. After the reaction was complete, the reaction mix-
ture was cooled to 0 ꢁC and methanol (10 mL) was slowly
added to quench the reaction. The reaction solvent was
evaporated under reduced pressure. The crude mixture
was purified by silica gel column chromatography (hex-
ane/EtOAc = 1:1) to give compound 13 (109 mg, 0.629
4.5. (3S,4S,5R)-5-Hydroxymethyl-3,4-isopropylidenedioxy-
pyrrolidin-2-one 12
To a solution of acetonide syn-8 (305 mg, 0.644 mmol) in
MeOH (20 mL) was added Pd(OH)2/C (29 mg, 0.193
mmol, 20 wt % Pd). The reaction mixture was stirred under
a H2 balloon for 40 h. The reaction mixture was then
filtered through a Celite pad to remove Pd(OH)2/C. The fil-
trate was concentrated under reduced pressure. The crude
product was purified by silica gel column chromatography
(DCM/MeOH = 10:1) to give c-lactam 12 as a white solid
mmol, quantitative) as a white solid. Rf = 0.3 (hexane/
25
EtOAc = 1:1); mp 92 ꢁC; ½aꢀD ¼ ꢁ48:2 (c 0.12, CHCl3);
1H NMR d 1.33 (s, 3H), 1.51 (s, 3H), 2.64 (dd, 1H,
J = 3.5, 10.6), 2.74–2.81 (m, 1H), 2.82–2.92 (m, 1H), 3.50
(dd, 1H, J = 4.7, 13.9), 4.05–4.11 (m, 1H), 4.12–4.22 (m,
1H), 4.68 (br s, 1H), 4.75 (dd, 1H, J = 4.2, 5.5), 4.87 (t,
1H, J = 5.5); 13C NMR d 23.2, 25.6, 57.9, 59.4, 68.4,
77.9, 81.9, 111.5; HRMS (CI) calcd for C8H16NO3
[M+H]+: 174.1130; found, 174.1131.
(100 mg, 0.535 mmol, 83%). Rf = 0.11 (DCM/MeOH =
23
10:1); mp 122 ꢁC; ½aꢀD ¼ þ22:9 (c 0.71, MeOH); 1H
NMR (CD3OD) d 1.35 (s, 3H), 1.39 (s, 3H), 3.59–3.67
(m, 1H), 3.77–3.84 (m, 2H), 4.68 (d, 1H, J = 5.7), 4.80
(dd, 1H, J = 4.2, 5.7); 13C NMR (CD3OD) d 26.1, 27.3,
57.8, 61.7, 76.7, 79.4, 113.8, 176.7; HRMS (CI) calcd for
C8H14NO4 [M+H]+: 188.0923; found, 188.0923.
4.8. D-Iminolyxitol [(2R,3S,4R)-3,4-dihydroxy-2-hydroxy-
methylpyrrolidine] hydrochloride 1
To a solution of pyrrolidine 13 (15 mg, 0.087 mmol) in
MeOH (1 mL) was added an aq solution of 6 M HCl
(1 mL). Then the reaction mixture was stirred for 30 min
at room temperature. The solvent was evaporated under
reduced pressure to give D-iminolyxitol hydrochloride 1 as
4.6. (3S,4S,5R)-5-Benzyloxymethyl-3,4-isopropylidenedioxy-
pyrrolidin-2-one 11
To a mixture of syn-10 and anti-10 (135 mg, 0.304 mmol) in
MeOH (15 mL) were added Pd/C (120 mg, 0.010 mmol,
10 wt % Pd) and ammonium formate (110 mg, 1.74 mmol).
The reaction mixture was heated at reflux for 1 h. Then, the
resulting mixture was filtered through a Celite pad to
remove Pd/C. The filtrate was concentrated under reduced
pressure. The crude diastereomeric mixture was purified
and separated by silica gel column chromatography
(hexane/EtOAc = 1:1) to give both anti-11 (18 mg,
0.0649 mmol, 23%) and syn-11 (24 mg, 0.0865 mmol,
30%), respectively, as a white solid.
a white solid (14.7 mg, 0.087 mmol, quantitative). Mp
27
161–163 ꢁC [lit.9a mp 159–161 ꢁC]; ½aꢀD ¼ þ15:4 (c 0.56,
20
H2O) {lit.9a ½aꢀD ¼ þ19:8 (c 0.45, H2O); L-iminolyxitol: lit.9f
20
1
½aꢀD ¼ ꢁ13:2 (c 0.014, H2O)}; H NMR (D2O) d 3.18 (dd,
1H, J = 7.3, 12.1), 3.50 (dd, 1H, J = 7.3, 12.1), 3.68–3.74
(m, 1H), 3.86 (dd, 1H, J = 8.4, 12.1), 3.96 (dd, 1H,
J = 5.0, 12.1 Hz), 4.32 (t, 1H, J = 4.0), 4.47 (m, 1H); 13C
NMR (D2O) d 47.8, 58.4, 63.3, 70.6, 70.8; HRMS (CI) calcd
for C5H12NO3 [MꢁCl]+: 134.0817; found, 134.0817.
Acknowledgments
anti-11 Rf = 0.20 (hexane/EtOAc = 1:2); Mp 109–111 ꢁC;
28
½aꢀD ¼ þ14:4 (c 0.22, CHCl3); 1H NMR (400 MHz) d
We thank the BK 21 Project and Agency for Defence
Development of Korea for financial support. This work
was also supported by KOSEF through the Research
Center for Energy Conversion and Storage.
1.37 (s, 3H), 1.48 (s, 3H), 3.50 (d, 2H, J = 3.7), 3.80 (dt,
1H, J = 0.9, 3.7 Hz), 4.52 (s, 2H), 4.55 (dd, 1H, J = 0.9,
5.7), 4.62 (d, 1H, J = 5.7), 6.02 (br s, 1H), 7.27–7.38 (m,
5H); 13C NMR (100 MHz) d 25.7, 27.0, 57.8, 70.4, 73.6,
76.9, 77.8, 112.3, 127.6, 128.0, 128.5, 137.3, 174.6; HRMS
(CI) calcd for C15H20NO4 [M+H]+: 278.1392; found,
278.1393.
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syn-11 Rf = 0.14 (hexane/EtOAc = 1:2); Mp 109–111 ꢁC;
28
½aꢀD ¼ ꢁ4:8 (c 0.18, CHCl3); 1H NMR (400 MHz with
D2O) d 1.36 (s, 3H), 1.44 (s, 3H), 3.57 (t, 1H, J = 9.5),
3.78 (dd, 1H, J = 4.1, 9.5), 3.88–3.92 (m, 1H), 4.53 (d,
1H, J = 11.7), 4.58 (d, 1H, J = 11.7), 4.65 (d, 1H.
J = 6.0), 4.74 (dd, 1H, J = 5.0, 6.0), 7.27–7.39 (m, 5H);
13C NMR d 25.9, 26.9, 54.4, 69.6, 73.6, 75.0, 77.5, 113.1,
127.8, 128.0, 128.5, 137.4, 173.1; HRMS (CI) calcd for
C15H20NO4 [M+H]+: 278.1392; found, 278.1391.
4.7. (2R,3S,4R)-2-Hydroxymethyl-3,4-isopropylidenedioxy-
pyrrolidine 13
To a solution of c-lactam 12 (118 mg, 0.630 mmol) in THF
(15 mL) was added BH3ÆTHF (5.0 mL, 1.0 M in THF,
4. (a) Imashiro, R.; Sakurai, O.; Yamashita, T.; Horikawa, H.
Tetrahedron 1998, 54, 10657–10670; (b) Broady, S. D.;