8272
K.-D. Lee et al. / Tetrahedron 57 -2001) 8267±8276
and amine in CH2Cl2 330 mL). The resultant solution was
stirred for 8 h until all the starting nitrile was consumed on
TLC. The reaction mixture was poured into ice±water and
the resulting solution was neutralized with cold sat.
NaHCO3 solution. The reaction product was extracted
with EtOAc 350 mL£3) and the organic layer was washed
with 100 mL of water and brine, dried over anhydrous
MgSO4, ®ltered and concentrated under reduced pressure.
The crude product was puri®ed by ¯ash column chroma-
tography to give product. Product for chemical analysis was
obtained as colorless oil by short path vacuum distillation
except 10 and 100.
9.15; N, 5.09. Found: C, 73.7; H, 8.96; N, 5.32. For 90
24
1
[a]D 9.1 3c5.0 in CH2Cl2) H NMR d 1.11 33H, t,
J7.0 Hz), 1.20 33H, d, J6.2 Hz), 2.02±2.13 32H, m),
2.54 31H, q, J6.6 Hz), 2.75±3.02 32H, m), 3.96±4.13
32H, m), 7.03±7.29 310H, m); 13C NMR d 14.1, 23.6,
34.4, 42.2, 48.3, 60.7, 69.4, 126.3, 126.4, 126.9, 128.2,
128.4, 128.8, 138.8, 143.5, 169.4. [HREIms. Found:
275.1891. C17H25NO23M1) requires: 275.1885].
4.1.5. Ethyl .2R,3R)-3-phenyl-1-[.R)-1-phenylethyl]aziri-
dine-2-carboxylate .10) and ethyl .2S,3S)-3-phenyl-1-
[.R)-1-phenylethyl]aziridine-2-carboxylate .100). Rf 3n-
Hex/Ether, 2:1) 0.40 for 10 and 0.52 for 100. For 10, solid,
mp 87±898C, [a]D 251.0 3c5.0 in CH2Cl2), 1H NMR d
24
4.1.1. Ethyl cis-3-benzyl-1-benzylaziridine-2-carboxyl-
1
ate .5). H NMR d 1.28 33H, t, J7.2 Hz), 2.21 31H, q,
1.00 33H, t, J7.0 Hz), 1.57 33H, d, J6.6 Hz), 2.64 31H, d,
J7.0 Hz), 2.86 31H, q, J6.6 Hz), 3.01 31H, d, J6.6 Hz),
3.99 32H, q J7.0 Hz), 7.17±7.50 310H, m); 13C NMR d
13.9, 22.9, 46.0, 47.3, 60.6, 69.7, 126.9, 127.1, 127.2, 127.6,
127.7, 128.3, 135.1, 143.2, 168.2. Anal. Calcd for
C19H21NO2: C, 77.3; H, 7.17; N, 4.74. Found: C, 77.6; H,
7.41; N, 4.69. For 100, solid, mp 64±668C, 1H NMR d 1.13
33H, t, J7.0 Hz), 1.52 33H, d, J6.5 Hz), 2.55 31H, d,
J6.9 Hz), 2.93 31H, q, J6.6 Hz), 3.13 31H, d, J
6.9 Hz), 3.87±4.15 32H, m), 7.03±7.29 310H, m). Anal.
Calcd for C19H21NO2: C, 77.3; H, 7.17; N, 4.74. Found:
C, 77.4; H, 7.37; N, 4.66.
J6.4 Hz), 2.33 31H, d, J7.0 Hz), 2.87 31H, dd J4.6,
5.7 Hz), 3.18 31H, dd, J6.6, 14.4 Hz), 3.63 32H, dd, J
13.6, 20.0 Hz), 4.24 32H, q, J7.2 Hz), 7.15±7.42 310H, m);
13C NMR d 14.2, 33.9, 42.3, 47.3, 60.9, 63.5, 126.2, 127.1,
127.9, 128.2, 128.3, 128.6, 137.6, 138.6, 169.6. Anal. Calcd
for C19H21NO2: C, 77.3; H, 7.17; N, 4.74. Found: C, 77.6; H,
7.24; N, 4.89.
4.1.2. Methyl cis-3-benzyl-1-benzylaziridine-2-carboxy-
1
late .6). H NMR d 2.09 31H, q, J6.2 Hz), 2.26 31H, d,
J7.0 Hz), 2.72 31H, dd J4.8, 5.4 Hz), 2.95 31H, dd,
J6.2, 14.2 Hz), 3.55 32H, dd, J13.6, 20.0 Hz), 3.70
33H, s), 7.05±7.24 310H, m); 13C NMR d 34.0, 42.2, 47.3,
52.1, 63.6, 126.3, 127.2, 128.0, 128.3, 128.4, 128.6, 137.5,
138.6, 170.1. Anal. Calcd for C18H19NO2: C, 76.8; H, 6.81;
N, 4.98. Found: C, 76.6; H, 6.77; N, 4.79.
4.1.6. Ethyl .2S,3S)-3-methyl-1-[.S)-1-phenylethyl]aziri-
dine-2-carboxylate .12) and ethyl .2R,3R)-3-methyl-1-
[.S)-1-phenylethyl]aziridine-2-carboxylate .120). Rf 3n-
Hex/Ether, 1:2) 0.64 for 120 and 0.54 for 12. For 12,
24
1
[a]D 256.8 3c5.0 in CH2Cl2), H NMR d 1.15 33H, t,
J5.4 Hz), 1.27 33H, t, J7.0 Hz), 1.42 33H, d, J6.6 Hz),
1.85 31H, q, J6.6 Hz), 2.21 31H, d, J6.6 Hz), 2.61 31H, q,
J6.6 Hz), 4.14 32H, q, J6.6 Hz), 7.18±7.39 35H, m); 13C
NMR d 13.0, 14.2, 22.8, 40.9, 42.9, 60.6, 69.6, 126.5, 126.8,
128.1, 143.6, 169.6. [HREIms. Found: 233.1421.
C14H19NO23M1) requires: 233.1416]. Anal. Calcd for
C14H19NO2: C, 72.1; H, 8.21; N, 6.00. Found: C, 72.4; H,
4.1.3. Ethyl .2S,3S)-3-benzyl-1-[.S)-1-phenylethyl]aziri-
dine-2-carboxylate .7) and ethyl .2R,3R)-3-benzyl-1-
[.S)-1-phenylethyl]aziridine-2-carboxylate .70). Rf 3n-
Hex/Ether, 3:1) 0.56 for 7 and 0.63 for 70. For 7,
24
[a]D 236.8 3c5.0 in CH2Cl2), 1.30 33H, t, J7.0 Hz),
1.48 33H, d, J6.6 Hz), 2.11 31H, q, J6.6 Hz), 2.32 31H, d,
J6.6 Hz), 2.68 31H, q, J6.6 Hz), 2.89 32H, m), 4.26 32H,
q, J7.0 Hz), 6.95±7.37 310H, m); 13C NMR d 14.10,
22.45, 33.75, 42.42, 46.71, 60.77, 69.50, 125.88, 126.79,
127.01, 128.05, 128.09, 128.34, 138.40, 142.98, 169.63.
Anal. Calcd for C20H23NO2: C, 77.6; H, 7.49; N, 4.53.
8.38; N, 5.84. For 120 [a]D 121.1 3c5.0 in CH2Cl2) 1H
24
NMR d 1.18 33H, t, J7.0 Hz), 1.33 33H, d, J7.0 Hz),
1.42 33H, d, J6.6 Hz), 1.95±2.09 32H, m), 2.62 31H, q,
J6.6 Hz), 4.04±4.20 32H, m), 7.18±7.39 35H, m); 13C
NMR d 13.4, 14.1, 23.5, 42.0, 42.3, 60.5, 69.4, 126.3,
126.8, 128.1, 143.5, 169.3. [HREIms. Found: 233.1427.
C14H19NO23M1) requires: 233.1416]. Anal. Calcd for
C14H19NO2: C, 72.1; H, 8.21; N, 6.00. Found: C, 72.2; H,
8.25; N, 5.72.
24
Found: C, 77.4; H, 7.44; N, 4.59. For 70 [a]D 19.1 3c
5.0 in CH2Cl2) 1H NMR d 1.11 33H, t, J7.0 Hz), 1.20 33H,
d, J6.2 Hz), 2.02±2.13 32H, m), 2.54 31H, q, J6.6 Hz),
2.75±3.02 32H, m), 3.96±4.13 32H, m), 7.03±7.29 310H,
m); 13C NMR d 14.1, 23.6, 34.4, 42.2, 48.3, 60.7, 69.4,
126.3, 126.4, 126.9, 128.2, 128.4, 128.8, 138.8, 143.5,
169.4. Anal. Calcd for C20H23NO2: C, 77.6; H, 7.49; N,
4.53. Found: C, 77.3; H, 7.56; N, 4.32.
4.1.7. Ethyl .2S,3S)-3-benzyloxymethyl-1-[.S)-1-phenyl-
ethyl]aziridine-2-carboxylate .13) and ethyl .2R,3R)-3-
methoxymethyl-1-[.S)-1-phenylethyl]-aziridine-2-carb-
oxylate .130). Rf 3n-Hex/Ether, 1:2) 0.63 for 13 and 0.56 for
130. For 13, 1H NMR d 1.30 33H, t, J7.0 Hz), 1.48 33H, d,
J6.6 Hz), 2.11 31H, q, J6.6 Hz), 2.32 31H, d, J6.6 Hz),
2.68 31H, q, J6.6 Hz), 2.89±2.95 32H, m), 4.26 32H, q,
J7.0 Hz), 6.95±7.37 312H, m); 13C NMR d 14.1, 22.5,
33.8, 42.4, 46.7, 60.8, 69.5, 125.9, 126.8, 127.0, 128.1,
128.1, 128.3, 138.4, 143.0, 169.6. Anal. Calcd for
C21H25NO3: C, 74.3; H, 7.42; N, 4.13. Found: C, 74.1; H,
4.1.4. Ethyl .2S,3S)-3-iso-butyl-1-[.S)-1-phenylethyl]-
aziridine-2-carboxylate .9) and ethyl .2R,3R)-3-iso-
butyl-1-[.S)-1-phenylethyl]aziridine-2-carboxylate .90).
Rf 3n-Hex/Ether, 1:2) 0.56 for 9 and 0.65 for 90. For 9
24
[a]D 236.8 3c5.0 in CH2Cl2), 1.30 33H, t, J7.0 Hz),
1.48 33H, d, J6.6 Hz), 2.11 31H, q, J6.6 Hz), 2.32 31H, d,
J6.6 Hz), 2.68 31H, q, J6.6 Hz), 2.89 32H, m), 4.26 32H,
q, J7.0 Hz), 6.95±7.37 310H, m); 13C NMR d 14.1, 21.4,
22.7, 28.4, 36.0, 42.7, 44.8, 60.5, 69.5, 126.8, 127.0, 128.0,
143.3, 170.0. [HREIms. Found: 275.1889. C17H25NO23M1)
requires: 275.1885]. Anal. Calcd for C17H25NO2: C, 74.1; H,
1
7.52; N, 4.29. For 130, H NMR d 1.11 33H, t, J7.0 Hz),
1.20 33H, d, J6.2 Hz), 2.02±2.13 32H, m,), 2.54 31H, q,
J6.6 Hz), 2.75±3.02 32H, m), 3.96±4.13 32H, m), 7.03±