S. Sugiyama et al. / Tetrahedron: Asymmetry 14 (2003) 2153–2160
2159
saturated aqueous sodium carbonate (30 mL), dried
over magnesium sulfate, filtered and concentrated in
vacuo. The residue was chromatographed on silica gel
(hexane:ethyl acetate=1:1) to give 6 (95 mg, 50%).
(m, 5H, Ph). IR (CHCl3) 2920, 2850, 1100 cm−1. MS
(EI) m/z: 309 (M+, 0.5), 279 (13), 278 (54), 174 (14), 164
(90), 105 (100). HRMS calcd for C17H31NO2Si:
309.2124. Found: 309.2122.
1
Yellowish oil. [h]D28=+31.4 (c 1.1, CHCl3). H NMR
(300 MHz, CDCl3) l: 1.46 (d, J=6.6 Hz, 3H, Me), 1.62
(d, J=6.4 Hz, 1H, NCHH), 1.90–1.97 (m, 2H, C2-H
and NCHH), 2.49 (q, J=6.6 Hz, 1H, PhCH), 3.79 (dd,
J=12, 3.5 Hz, 1H, OCHH), 4.56 (dd, J=12, 8.5 Hz,
1H, OCHH), 7.15–7.26 (m, 3H, Ph), 7.35 (m, 2H, Ph),
7.77 (d, J=9.2 Hz, 2H, nitrobenzoyl), 8.17 (d, J=9.2
Hz, 2H, nitrobenzoyl). IR (CHCl3) 1715 cm−1. EI-MS
m/z (%) 326 (M+, 9), 221 (15), 150 (46), 105 (100).
HRMS calcd for C18H18N2O4: 326.1266. Found:
326.1263.
Acknowledgements
The authors wish to thank the staff of the Analysis
Center of Meiji Pharmaceutical University for perform-
ing the elemental analysis (Miss Ayako Ohmae) and
mass spectra (Miss Tamami Koseki). We are also grate-
ful to Miss Satoko Ikoma and Miss Hiromi Mochizuki
for their technical assistance.
4.4.4. (2S,aR)-1-(a-Methylbenzyl)aziridinylmethanol 7.
According to the procedure for hydrolysis of 4, the
aziridine 7 (26 mg, 96%) was prepared from 6. The
spectrum data of 7 were good in agreement with the
reported data.12
References
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4.4.5.
(2R,aR)-3-(tert-Butyldimethylsilyl)oxy-2-(N-a-
methylbenzyl)aminopropyl 4-nitrobenzoate 8. A solution
of tert-butyldimethylsilyl chloride (105 mg, 0.70 mmol)
in DMF (0.5 mL) was added dropwise to a mixture of
(S)-2a (100 mg, 0.29 mmol) and imidazole (78 mg, 0.87
mmol) in DMF (0.5 mL) at room temperature. After
being stirred for 1 h, the reaction mixture was poured
into saturated aqueous ammonium chloride and
extracted with diethyl ether. The extracts were com-
bined, dried over magnesium sulfate, filtered and con-
centrated in vacuo. The residue was chromatographed
on silica gel (hexane:ethyl acetate=4:1) to give 8 (89
1
mg, 67%). Yellowish oil. [h]2D6=−0.8 (c 1.0, CHCl3). H
NMR (400 MHz, CDCl3) l: 0.05 (s, 3H, MeSi), 0.08 (s,
t
3H, MeSi), 0.91 (s, 9H, Bu), 1.34 (d, J=6.6 Hz, 3H,
PhCHMe), 2.86 (m, 1H, C2-H), 3.65 (dd, J=10, 3.4
Hz, 1H, OCHH), 3.78 (dd, J=10, 4.9 Hz, 1H, OCHH),
3.94 (q, J=6.6 Hz, 1H, PhCH), 4.24 (dd, J=15, 4.2
Hz, 1H, OCHH), 4.28 (dd, J=15, 4.6 Hz, 1H, OCHH),
7.21–7.70 (m, 5H, Ph), 8.13 (d, J=8.9 Hz, 2H,
nitrobenzoyl), 8.28 (d, J=8.9 Hz, 2H, nitrobenzoyl). IR
(CHCl3) 1723 cm−1. MS (EI) m/z: (%) 458 (M+, 0.7),
443 (5), 313 (75), 278 (14), 209 (10), 105 (100). HRMS
calcd for C24H34N2O5Si: 458.2237. Found: 458.2238.
4.4.6.
(2R,aR)-3-(tert-Butyldimethylsilyl)oxy-2-(N-a-
methylbenzyl)amino-1-propanol 9. A mixture of 8 (50
mg, 0.11 mmol) and potassium hydroxide (11.2 mg,
0.20 mmol) in 85% aqueous methanol (5.8 mL) was
stirred for 30 min at room temperature. The reaction
mixture was poured into saturated aqueous ammonium
chloride and extracted with ethyl acetate. The extracts
were combined, dried and concentrated in vacuo. The
residue was chromatographed on silica gel (hex-
ane:ethyl acetate=1:1) to give 9 (23 mg, 69%). Yellow-
ish oil. [h]2D6=−0.3 (c 0.46, CHCl3). 1H NMR (400
MHz, CDCl3) l: 0.06 (s, 3H, MeSi), 0.08 (s, 3H, MeSi),
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t
0.91 (s, 9H, Bu), 1.36 (d, J=6.6 Hz, 3H, Me), 2.60 (m,
1H, C2-H), 3.38 (d, J=5.6 Hz, 2H, OCH2), 3.53 (dd,
J=10, 4.2 Hz, 1H, OCHH), 3.74 (dd, J=10, 4.6 Hz,
1H, OCHH), 3.91 (q, J=6.6 Hz, 1H, PhCH), 7.21–7.52