L. Zhu et al. / Tetrahedron: Asymmetry 26 (2015) 6–15
13
4.5.12. (5S,20R,30S)-5-Isopropyl-3-phenyl-1-[20-methyl-30-(p-
methoxyphenylamino)-30-(m-nitro-phenyl)-propionyl]imidazoli-
din-2-thione 5c
4.5.16. (5S,20R,30S)-5-Isopropyl-3-phenyl-1-[20-methyl-30-(p-
methoxyphenylamino)-30-phenyl-butyryl]imidazolidin-2-thi-
one 5g
Yield: 86%; yellow solid; mp 88.7–89.4 °C; [
0.13, CH2Cl2); IR: 3300, 1682, 1598, 1530, 1486, 1188 cmꢀ1
NMR (400 MHz, CDCl3): 0.92 (d, J = 7.0 Hz, 3H), 0.95 (d,
a
]
D
20 = +155.1 (c
Yield: 88%; white solid; mp 137.6–138.4 °C; [
a]
20 = +165.2 (c
D
;
1H
0.11, CH2Cl2); IR: 3308, 1681, 1596, 1514, 1463, 1180 cmꢀ1 1H
;
d
NMR (400 MHz, CDCl3): d 0.70–0.93 (m, 9H), 1.19–1.33 (m, 1H),
1.68–1.83 (m, 1H), 2.31–2.43 (m, 1H), 3.57–3.65 (m, 4H), 3.99
(dd, J = 10.8, 8.9 Hz, 1H), 4.54 (d, J = 9.7 Hz, 1H), 4.75 (dq, J = 8.9,
1.8 Hz, 1H), 5.73 (dt, J = 15.6, 4.3 Hz, 1H), 6.49 (d, J = 8.8 Hz, 2H),
6.60 (d, J = 8.9 Hz, 2H), 7.13–7.19 (m, 1H), 7.22–7.28 (m, 2H),
7.32–7.50 (m, 7H); 13C NMR (100 MHz, CDCl3): d 11.71, 14.91,
17.95, 24.36, 29.68, 49.74, 50.41, 55.66, 61.24, 62.66, 114.53,
114.89, 126.28, 127.17, 127.78, 128.20, 128.39, 129.44, 139.65,
140.95, 142.02, 151.64, 177.13, 179.46; HRMS calcd for C30H35N3-
O2S [M+H]+: 502.2523, found 502.2504.
J = 7.2 Hz, 3H), 1.14 (d, J = 6.3 Hz, 3H), 2.34–2.51 (m, 1H), 3.67–
3.76 (m, 4H), 4.08–4.16 (m, 1H), 4.69 (d, J = 9.2 Hz, 1H), 4.77–
4.85 (m, 1H), d 5.88 (dt, J = 15.7, 7.2 Hz, 1H), 6.55 (d, J = 8.4 Hz,
2H), 6.69 (d, J = 8.4 Hz, 2H), 7.41–7.59 (m, 6H), 7.88 (d, J = 7.6 Hz,
1H), 8.11 (d, J = 8.3 Hz, 1H), 8.34 (s, 1H); 13C NMR (100 MHz,
CDCl3): d 15.11, 16.14, 18.16, 29.84, 42.27, 50.60, 55.81, 61.42,
63.62, 114.97, 115.11, 122.57, 122.85, 126.39, 128.51, 129.58,
129.66, 133.86, 139.76, 140.47, 144.74, 148.64, 152.39, 176.95,
179.58; HRMS calcd for C29H32N4O4S [M+H]+: 533.2217, found:
533.2226.
4.5.17. (5S,20R,30S)-5-Isopropyl-3-phenyl-1-[20-methyl-30-(p-
4.5.13. (5S,20R,30S)-5-Isopropyl-3-phenyl-1-[20-methyl-30-(p-
methoxyphenylamino)-30-(200,300-dimethoxyphenyl)-propionyl]
imidazolidin-2-thione 5d
methoxyphenylamino)-30-phenyl-valeryl]imidazolidin-2-thione
5h
Yield: 94%; white solid; mp 140.6–141.5 °C; [
a]
20 = +123.6 (c
D
Yield: 88%; white solid; mp 82.6–83.7 °C; [
a]
20 = +85.1 (c 0.58,
0.24, CH2Cl2); IR: 3310, 1681, 1596, 1514, 1463, 1184 cmꢀ1 1H
;
D
CH2Cl2); IR: 3312, 1682, 1596, 1514, 1480, 1185 cmꢀ1
;
1H NMR
NMR (400 MHz, CDCl3): d 0.78 (t, J = 7.0, 7.0 Hz, 3H), 0.82–0.90
(m, 6H), 1.11–1.31 (m, 3H), 1.70–1.84 (m, 1H), 2.31–2.46
(m, 1H), 3.57–3.65 (m, 4H), 3.98 (dd, J = 10.8, 8.9 Hz, 1H), 4.54 (d,
J = 9.8 Hz, 1H), 4.73 (dq, J = 8.9, 1.8 Hz, 1H), 5.78 (dt, J = 16.8,
3.6 Hz, 1H), 6.49 (d, J = 8.8 Hz, 2H), 6.60 (d, J = 8.9 Hz, 2H), 7.12–
7.19 (m, 1H), 7.22–7.28 (m, 2H), 7.32–7.49 (m, 7H); 13C NMR
(100 MHz, CDCl3): d 14.21, 15.15, 18.13, 20.60, 29.69, 33.23,
47.97, 50.39, 55.61, 61.28, 62.94, 114.49, 114.99, 126.25, 127.17,
127.80, 128.19, 128.37, 129.41, 139.61, 140.80, 141.90, 151.68,
177.17, 179.41; HRMS calcd for C31H37N3O2S [M+H]+: 516.2679,
found 516.2655.
(400 MHz, CDCl3): d 0.87 (d, J = 1.9 Hz, 3H), 0.89 (d, J = 1.6 Hz,
3H), 1.04 (d, J = 6.6 Hz, 3H), 2.31–2.45 (m, 1H), 3.62–3.67 (m,
4H), 3.81 (s, 3H), 3.92 (s, 3H), 4.04 (dd, J = 10.7, 9.1 Hz, 1H), 4.78
(dq, J = 9.1, 2.1 Hz, 1H), 5.03 (d, J = 10.2 Hz, 1H), 5.78 (dt, J = 16.8,
6.5 Hz, 1H), 6.59 (d, J = 9.0 Hz, 2H), 6.63 (d, J = 8.9 Hz, 2H), 6.71–
7.13 (m, 3H), 7.35–7.56 (m, 5H); 13C NMR (100 MHz, CDCl3): d
15.03, 15.93, 18.16, 29.56, 42.38, 550.33, 55.68, 55.71, 61.08,
61.19, 111.25, 114.54, 114.57, 115.31, 120.11, 124.16, 126.44,
128.26, 129.53, 129.56, 139.91, 147.83, 151.92, 152.35, 178.12,
179.56; HRMS calcd for C31H37N3O4S [M+H]+: 548.2578, found:
548.2590.
4.5.18. (5S,20R,30S)-5-Isopropyl-3-phenyl-1-[20-methyl-30-(p-
4.5.14. (5S,20R,30S)-5-Isopropyl-3-phenyl-1-[20-methyl-30-(p-
methoxyphenylamino)-30-(200-furyl)-propionyl]imidazolidin-2-
thione 5e
methoxyphenylamino)-30-phenyl-isovaleryl]imidazolidin-2-thione
5i
Yield: 65%; white solid; mp 87.9–89.2 °C; [
a]
20 = +196.7 (c 0.21,
D
Yield: 68%; white solid; mp 76.2–77.4 °C; [
a]
20 = +148.3 (c 0.15,
CH2Cl2); IR: 3310, 1681, 1597, 1513, 1463, 1183 cmꢀ1 1H NMR
;
D
CH2Cl2); IR: 3297, 1680, 1596, 1513, 1499, 1191 cmꢀ1
;
1H NMR
(400 MHz, CDCl3): d 0.63 (d, J = 6.8 Hz, 3H), 0.82 (d, J = 7.0 Hz,
3H), 0.95 (d, J = 6.8 Hz, 3H), 1.07 (d, J = 6.8 Hz, 1H), 1.85–1.98 (m,
1H), 2.14–2.26 (m, 1H), 3.50 (dd, J = 10.9, 1.9 Hz, 1H), 3.61
(s, 3H), 3.88 (dd, J = 10.8, 8.8 Hz, 1H), 4.64–4.71 (m, 1H), 4.77
(d, J = 8.3 Hz, 1H), 6.12 (dt, J = 14.2, 5.8 Hz, 1H), 6.49 (d, J = 8.9 Hz,
2H), 6.62 (d, J = 8.9 Hz, 2H), 7.09–7.16 (m, 1H), 7.19–7.46 (m,
9H); 13C NMR (100 MHz, CDCl3): d 14.56, 18.01, 18.90, 20.71,
29.06, 29.54, 49.87, 51.69, 55.44, 59.03, 60.66, 114.22, 114.54,
126.14, 126.87, 127.55, 127.91, 128.18, 129.21, 139.57, 141.24,
141.58, 151.31, 176.14, 179.17; HRMS calcd for C31H37N3O2S
[M+H]+: 516.2679, found 516.2659.
(400 MHz, CDCl3): d 0.92 (d, J = 1.4 Hz, 3H), 0.94 (d, J = 1.0 Hz,
3H), 1.25 (d, J = 6.6 Hz, 1H), 2.36–2.47 (m, 1H), 3.71–3.76 (m,
4H), 4.05 (dd, J = 9.7, 9.6 Hz, 1H), 4.81 (dq, J = 9.0, 2.0 Hz, 1H),
4.87 (d, J = 9.5 Hz, 1H), 5.95 (dt, J = 16.0, 6.6 Hz, 1H), 6.64 (d,
J = 8.8 Hz, 2H), 6.74 (d, J = 8.8 Hz, 2H), 6.89–7.23 (m, 3H), 7.38–
7.59 (m, 5H); 13C NMR (100 MHz, CDCl3): d 14.97, 16.03, 18.04,
29.42, 43.01, 50.08, 55.51, 59.52, 60.94, 114.45, 115.01, 126.21,
126.44, 129.35, 139.57, 140.89, 141.60, 146.75, 146.89, 151.90,
152.13, 177.06, 179.20; HRMS calcd for C27H31N3O3S [M+H]+:
478.2159, found: 478.2147.
4.5.15. (5S,20R,30S)-5-Isopropyl-3-phenyl-1-[20-methyl-30-(p-
methoxyphenylamino)-30-(200-thienyl)-propionyl]imidazolidin-
2-thione 5f
4.5.19. (5S,20R,30S)-5-Isopropyl-3-phenyl-1-[20-methyl-30-(p-meth-
oxyphenylamino)-30-phenyl-hexanoyl]imidazolidin-2-thione 5j
Yield: 92%; white solid; mp 162.1–162.9 °C; [
a]
20 = +157.1 (c
D
Yield: 80%; white solid; mp 74.6–76.0 °C; [
a]
20 = +133.3 (c 0.40,
0.13, CH2Cl2); IR: 3311, 1681, 1597, 1514, 1464, 1182 cmꢀ1 1H
;
D
CH2Cl2); IR: 3307, 1682, 1597, 1514, 1486, 1187 cmꢀ1
;
1H NMR
NMR (400 MHz, CDCl3): d 0.76 (t, J = 4.7, 4.7 Hz, 3H), 0.83–0.90
(m, 6H), 1.09–1.24 (m, 5H), 1.70–1.84 (m, 1H), 2.32–2.45 (m,
1H), 3.59–3.66 (m, 4H), 4.00 (dd, J = 10.9, 8.9 Hz, 1H), 4.53 (d,
J = 9.8 Hz, 1H), 4.74 (dq, J = 9.0, 1.8 Hz, 1H), 5.76 (dt, J = 17.2,
2.9 Hz, 1H), 6.49 (d, J = 8.9 Hz, 2H), 6.60 (d, J = 8.9 Hz, 2H), 7.12–
7.18 (m, 1H), 7.22–7.29 (m, 2H), 7.34–7.51 (m, 7H); 13C NMR
(100 MHz, CDCl3): d 13.90, 15.13, 17.98, 22.56, 29.45, 30.81,
48.04, 50.43, 55.56, 61.29, 62.59, 114.52, 114.96, 126.25, 127.15,
127.81, 128.21, 128.36, 129.41, 139.65, 140.91, 142.00, 151.68,
177.20, 179.46; HRMS calcd for C32H39N3O2S [M+H]+: 530.2836,
found 530.2832.
(400 MHz, CDCl3): d 0.86 (d, J = 5.6 Hz, 3H), 0.88 (d, J = 5.4 Hz,
3H), 1.13 (d, J = 6.6 Hz, 1H), 2.27–2.43 (m, 1H), 3.62–3.70 (m,
4H), 4.02 (dd, J = 10.7, 9.2 Hz, 1H), 4.67 (d, J = 9.7 Hz, 1H), 4.75
(dq, J = 9.2, 2.2 Hz, 1H), 5.87 (dt, J = 16.4, 8.0 Hz, 1H), 6.20–6.26
(m, 2H), 6.59 (d, J = 8.6 Hz, 2H), 6.67 (d, J = 9.0 Hz, 2H), 7.28–7.30
(m, 1H), 7.33–7.50 (m, 5H); 13C NMR (100 MHz, CDCl3): d 15.04,
15.50, 17.99, 29.37, 41.23, 50.16, 55.69, 57.87, 60.93, 107.77,
110.13, 114.54, 114.63, 115.72, 126.32, 128.20, 129.48, 139.77,
141.85, 152.46, 154.42, 177.22, 179.24; HRMS calcd for C27H31N3-
O2S2 [M+H]+: 494.1930, found: 494.1931.