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K. Ishii et al. / Tetrahedron 62 (2006) 10865–10878
J¼7.4 Hz, OCH2CH3 for c), 1.34 (s, 9H, CMe3 for b), 1.44
(s, 9H, CMe3 for c), 1.65 (ddd, 1H, J¼13.1, 4.3, 4.0 Hz, H-40
for b), 1.83–1.88 (m with dt-character, 1H, J¼12.8, 5 Hz, H-
40 for c), 2.30 (ddd, 1H, J¼12.8, 10.4, 7.6 Hz, H-40 for c),
2.53 (td, 1H, J¼13.1, 9.2 Hz, H-40 for b), 2.64–2.69 (m
with quintet character, 1H, J¼5 Hz, H-30 for c), 3.19–3.25
(m, 3H, H-30 for b and H-50 for b and c), 3.50, 3.79 (each
d, 4H, J¼14 Hz, CH2Ph for b and c), 3.72 (dd, 1H, J¼10,
7.6 Hz, H-20 for b), 3.75 (dd, 1H, J¼8.9, 5.2 Hz, H-20 for
c), 4.19 (q, 4H, J¼7.3 Hz, OCH2 for b and c), 5.75 (d,
1H, J¼15.6 Hz, H-2 for b), 5.88 (d, 1H, J¼15.6 Hz, H-2
for c), 6.84 (dd, 1H, J¼15.6, 10 Hz, H-3 for b), 6.87 (dd,
1H, J¼15.6, 8.9 Hz, H-3 for c), 7.19–7.32 (m, 10 H, Ph
for b and c); 13C NMR (100 MHz): d 14.4 (q, OCH2CH3
for b and c), 16.7 (q, 50-Me for c), 19.6 (q, 50-Me for b),
28.1 (q, CMe3 for b and c), 33.6 (t, C-40 for b), 34.8 (t,
C-40 for c), 46.9 (d, C-30 for b), 49.1 (d, C-30 for c), 51.3,
51.9 (t, CH2Ph for b and c), 54.7, 55.3 (d, C-50 for
b and c), 60.3, 60.4 (t, OCH2 for b and c), 64.2, 65.1 (d,
C-20 for b and c), 80.7 (s, CMe3 for b and c), 123.2 (d,
C-2 for c), 124.9 (d, C-2 for b), 126.6, 127.9, 128.0,
128.1, 128.3 (5d, 10C in Ph for b and c), 139.3 (s, 2C in
Ph for b and c), 144.3 (d, C-3 for b), 148.1 (d, C-3 for c),
165.4, 166.0 (s, C-1 for b and c), 170.9, 172.8 (s, CO2 for
b and c).
8 Hz, H-3), 7.03–7.47 (m, 10H, 2Ph); 13C NMR
(100 MHz): d 14.4 (q, OCH2CH3), 28.1 (q, CMe3), 37.7 (t,
C-40), 47.8 (d, C-30), 54.1 (t, CH2Ph), 60.2 (t, OCH2),
64.2, 66.9 (2d, C-20, C-50), 81.0 (s, CMe3), 122.6 (d, C-2),
126.9, 127.3, 127.6, 127.8, 128.4, 129.8 (6d, 10C in 2Ph),
136.3 (s, C in CH2Ph), 141.9 (s, C in 50-Ph), 147.3 (d,
C-3), 165.8 (C-1), 170.8 (s, CO2); EI-MS m/z 435 (M+,
6%), 378 (10), 362 (6), 344 (24), 334 (7), 288 (34), 216
(11), 104 (8), 91 (100), 57 (13); HRMS calcd for
C27H33NO4: 435.2410, found: 435.2415.
4.5.2. Ethyl (E,20RS,30RS,50SR)-3-(1-benzyl-3-tert-butyl-
oxycarbonyl-5-phenylpyrrolidin-2-yl)acrylate [(E)-22b].
An oil; IR (CHCl3): 1715 cmꢀ1 (C]O); 1H NMR
(500 MHz): d 1.29 (t, 3H, J¼7.2 Hz, OCH2CH3), 1.34 (s,
9H, CMe3), 1.97 (ddd, 1H, J¼13.7, 9.8, 5.5 Hz, H-40),
2.84 (td, 1H, J¼13.7, 9.8 Hz, H-40), 3.38–3.42 (m, 1H, H-
30), 3.40, 3.60 (each d, 2H, J¼13.7 Hz, CH2Ph), 3.93 (dd,
1H, J¼10.5, 7.0 Hz, H-20), 4.14 (dd, 1H, J¼9.8, 5.5 Hz,
H-50), 4.22 (q, 2H, J¼7.2 Hz, OCH2), 5.72 (d, 1H,
J¼15.6 Hz, H-2), 6.97 (dd, 1H, J¼15.6, 10.5 Hz, H-3),
7.20–7.50 (10H, m, 2Ph); 13C NMR (100 MHz): d 14.4 (q,
OCH2CH3), 28.1 (q, CMe3), 35.3 (t, C-40), 47.4 (d, C-30),
51.7 (t, CH2Ph), 60.4 (t, OCH2), 63.4, 65.0 (2d, C-20,
C-50), 80.9 (s, CMe3), 125.8 (d, C-2), 126.7, 127.1, 127.4,
128.0, 128.3, 128.4 (6d, 10C in 2Ph), 138.7 (s, C in
CH2Ph), 142.8 (d, C-3), 144.0 (s, C in 50-Ph), 165.3 (C-1),
170.5 (s, CO2); EI-MS m/z 435 (M+, 6%), 378 (41), 362
(14), 344 (100), 288 (86), 216 (15), 91 (80); HRMS calcd
for C27H33NO4: 435.2410, found: 435.2412.
4.4.8. Ethyl (Z)-5-[(E)-N-benzylideneamino]-3-hexenoate
(21). An oil; IR (CHCl3): 1720 (C]O), 1635 cmꢀ1 (C]N);
1H NMR (400 MHz): d 1.24 (t, 3H, J¼7.1 Hz, OCH2CH3),
1.35 (d, 3H, J¼6.6 Hz, 3H-3), 3.17 (ddd, 2H, J¼7.3, 3.4,
1.7 Hz, 2H-2), 4.13 (q, 2H, J¼7.1 Hz, OCH2), 4.25–4.33
(m, 1H, H-5), 5.66 (dtd, 1H, J¼11.0, 7.3, 1.0 Hz, H-3),
5.78–5.85 (m with ddt-character, 1H, J¼11, 8, 2 Hz, H-4),
7.37–7.42, 7.71–7.74 (each m, 5H, Ph), 8.31 (s, 1H,
N]CH); 13C NMR (100 MHz): d 14.3 (q, OCH2CH3),
23.2 (q, C-6), 33.6 (t, C-2), 60.7 (t, OCH2), 62.9 (d,
C-5), 120.9 (d, C-3), 128.0, 128.4, 130.4 (3, 5C in Ph),
135.9 (d, C-4), 136.1 (s, C in Ph), 159.3 (d, N]C), 171.2
(s, C-1); EI-MS m/z 245 (M+, 16%), 230 (6), 200 (16), 172
(31), 158 (100), 131 (11), 106 (23), 91 (27), 67 (15), 55
(11); HRMS calcd for C15H19NO2: 245.1416, found:
245.1417.
4.5.3. Ethyl (E,20RS,30SR,50RS)-3-(1-benzyl-3-tert-butyl-
oxycarbonyl-5-phenylpyrrolidin-2-yl)acrylate [(E)-22c].
An oil; IR (CHCl3): 1710 cmꢀ1 (C]O); 1H NMR
(400 MHz): d 1.28 (t, 3H, J¼7.1 Hz, OCH2CH3), 1.39 (s,
9H, CMe3), 1.88–1.96 (m, 1H, H-40), 2.35 (ddd, 1H,
J¼12.5, 8, 5 Hz, H-40), 2.72–2.79 (m, 1H, H-30), 3.47,
3.76 (each d, 2H, J¼13.7 Hz, CH2Ph), 3.53–3.56 (m with
t-character, 1H, J¼8 Hz, H-20), 3.78–3.82 (m with t-charac-
ter, 1H, J¼8 Hz, H-50), 4.16 (q, 2H, J¼7.1 Hz, OCH2), 5.90
(d, 1H, J¼15.6 Hz, H-2), 6.79 (dd, 1H, J¼15.6, 7.8 Hz,
H-3), 7.07–7.47 (m, 10H, 2Ph); 13C NMR (100 MHz):
d 14.4 (q, OCH2CH3), 28.2 (q, CMe3), 37.8 (t, C-40), 49.0
(d, C-30), 54.9 (t, CH2Ph), 60.3 (t, OCH2), 66.8, 67.3 (2d,
C-20, C-50), 80.9 (s, CMe3), 121.9 (d, C-2), 126.9, 127.2,
127.4, 127.8, 128.4, 129.7 (6d, 10C in 2Ph), 136.5 (s, C in
CH2Ph), 142.6 (s, C in 50-Ph), 149.3 (d, C-3), 166.0 (C-1),
172.6 (s, CO2); EI-MS m/z 435 (M+, 37%), 378 (68), 362
(21), 344 (44), 334 (9), 306 (26), 288 (48), 202 (9), 91
(100); HRMS calcd for C27H33NO4: 435.2410, found:
435.2404.
4.5. Reactions of 3-phenylaziridines 5 and 6 with alkenes
A 0.060 mol Lꢀ1 solution of aziridines 5 and 6 in dry aceto-
nitrile with 10 equiv of tert-butyl acrylate was irradiated
with a low-pressure mercury lamp in a quartz test tube at
room temperature. After removal of the solvent, flash col-
umn chromatography afforded the adducts. A 0.060 mol Lꢀ1
solution of aziridines 5 and 6 in xylene with 10 equiv of tert-
butyl acrylate was heated under reflux. The results are sum-
marized in Table 2.
4.5.4. Ethyl (2E,20RS,30SR,50SR)-3-(1-benzyl-3-tert-butyl-
oxycarbonyl-5-phenylpyrrolidin-2-yl)acrylate [(E)-22d].
1
4.5.1. Ethyl (E,20RS,30RS,50RS)-3-(1-benzyl-3-tert-butyl-
oxycarbonyl-5-phenylpyrrolidin-2-yl)acrylate [(E)-22a].
An oil; IR (CHCl3): 1710 cmꢀ1 (C]O); 1H NMR
(500 MHz): d 1.26 (t, 3H, J¼7.0 Hz, OCH2CH3), 1.39 (s,
9H, CMe3), 2.17 (t, 2H, J¼8.5 Hz, H-40), 2.99–3.06 (m
with q-character, 1H, J¼9 Hz, H-30), 3.45, 3.75 (each d,
2H, J¼14.0 Hz, CH2Ph), 3.67–3.73 (m with q-character,
2H, J¼8 Hz, H-20, H-50), 4.15 (q, 2H, J¼7.0 Hz, OCH2),
5.87 (dd, 1H, J¼15.6, 0.6 Hz, H-2), 6.78 (dd, 1H, J¼15.6,
An oil; IR (CHCl3): 1720, 1715 cmꢀ1 (C]O); H NMR
(500 MHz): d 1.30 (t, 3H, J¼7.2 Hz, OCH2CH3), 1.45 (s,
9H, CMe3), 2.33 (ddd, 1H, J¼13.4, 7.5, 5 Hz, H-40), 2.59
(ddd, 1H, J¼13.4, 9.5, 8.2 Hz, H-40), 2.74 (ddd, 1H,
J¼9.5, 5, 2.7 Hz, H-30), 3.33, 3.60 (each d, 2H, J¼
14.0 Hz, CH2Ph), 4.01–4.05 (m with t-character, 1H, J¼
8 Hz, H-50), 4.08 (dd, 1H, J¼9.8, 2.7 Hz, H-20), 4.22 (q,
2H, J¼7.2 Hz, OCH2), 5.74 (d, 1H, J¼15.6 Hz, H-2), 7.00
(dd, 1H, J¼15.6, 9.8 Hz, H-3), 7.20–7.40 (m, 10H, 2Ph);