B. Bdiri, Z.-M. Zhou / Tetrahedron Letters xxx (2017) xxx–xxx
7
(20S, 40R, 50R)-Ethyl 40-(4-bromophenyl)-1,3-dioxo-20-phenyl-1,3-
dihydrospiro[indene-2,30-pyrrolidine]-50- carboxylate 3b
ralpak column AD-H, hexane/2-propanol = 70/30, flow rate = 1 mL/
min) tR = 19.15 min, 22.95 min.
Light yellow sticky oil: Yield = 60% (120 mg); ee = ꢀ74.6%. 1H
NMR (400 MHz, CDCl3) d 7.69 (dd, J = 7.6, 3.5 Hz, 1H), 7.55–7.43
(m, 2H), 7.41–7.37 (m, 1H), 7.16 (t, J = 8.5 Hz, 2H), 7.11–7.05 (m,
3H), 7.04–6.94 (m, 5H), 5.07 (s, 1H), 4.91 (d, J = 9.9 Hz, 1H), 4.32
(d, J = 9.9 Hz, 1H), 4.07 (q, 7.2 Hz), 3.08 (br, 1H), 1.06 (t, 7.2 Hz).
13C NMR (101 MHz, CDCl3) d 198.40, 198.15, 172.54, 141.17,
141.07, 135.13, 134.74, 134.41, 133.74, 130.47, 127.48, 127.10,
125.65, 121.64, 121.53, 120.62, 69.76, 61.93, 60.27, 56.67, 55.59,
(20R, 40R, 50S)-Ethyl 20-(1-bromonaphthalen-2-yl)-40-(3-nitrophenyl)-
1,3-dioxo-1,3-dihydrospiro[indene-2,30-pyrrolidine]-50-carboxylate 3f
White crystal: Yield = 73% (174 mg); ee = ꢀ81.4%. mp = 240–
241 °C. 1H NMR (400 MHz, CDCl3) d 8.24 (d, J = 8.5 Hz, 1H), 8.11
(s, 1H), 8.00–7.92 (m, 1H), 7.87 (dd, J = 17.2, 8.3 Hz, 2H), 7.80 (t,
J = 7.1 Hz, 1H), 7.71 (t, J = 9.0 Hz, 1H), 7.60–7.48 (m, 2H), 7.46–
7.32 (m, 3H), 7.26–7.16 (m, 2H), 5.84 (s, 1H), 5.09 (d, J = 10.4 Hz,
1H), 4.32 (d, J = 10.2 Hz, 1H), 4.10 (dd, J = 13.5, 6.5 Hz, 2H), 2.92
(br, 1H), 1.08 (t, J = 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) d
198.42, 197.00, 141.66, 140.70, 134.97, 134.73, 134.67, 134.17,
133.31, 128.25, 127.34, 126.63, 126.34, 126.32, 126.10, 125.69,
122.71, 122.43, 122.17, 122.03, 121.71, 67.26, 66.03, 61.73, 60.40,
13.09. IR (KBr)
t 2935, 1713, 1639, 1550, 1499, 1355, 1283,
1210, 1180, 1049, 937, 877, 700, 625 cmꢀ1. HRMS Calcd. For C27
-
-
H
23BrNO+4 [M+H]+: 504.0810; found: 504.0812. Calcd. For C27H23
rNO+4 [MꢀBr+H]+: 426.1705; found: 426.1714 (Chiralpak column
AD-H, hexane/2-propanol = 95/5, flow rate = 1 mL/min) tR = 20.0
min, 24.6 min.
54.07, 13.02. IR (KBr)
t 2925, 1721, 1698, 1589, 1527, 1495,
1346, 1256, 1087, 1011, 754, 565 cmꢀ1. HRMS Calcd. For C31H24
-
(20R, 40R, 50R)-Ethyl 40-(4-bromophenyl)-20-(2,4-dichlorophenyl)-1,3-
dioxo-1,3-dihydrospiro[indene-2,30-pyrrolidine]-50-carboxylate 3c
Light yellow crystal: Yield = 85% (189 mg); ee = ꢀ70.4%. mp =
273–274 °C. 1H NMR (400 MHz, CDCl3) d 7.88 (dd, J = 14.6, 8.1
Hz, 1H), 7.63 (d, J = 4.2 Hz, 2H), 7.24–7.21 (m, 3H), 7.19 (d, J =
2.3 Hz, 1H), 7.04–7.01 (m, 2H), 7.00 (d, J = 2.1 Hz, 1H), 6.90 (d, J
= 8.4 Hz, 1H), 5.11 (s, 1H), 4.63 (d, J = 8.0 Hz, 1H), 3.96 (d, J = 8.0
Hz, 1H), 3.37 (s, 3H), 2.99 (br, 1H). 13C NMR (101 MHz, CDCl3) d
199.50, 194.83, 169.66, 140.81, 139.73, 134.91, 134.81, 134.55,
133.75, 133.07, 132.96, 132.86, 132.23, 130.24, 130.18, 129.39,
127.72, 126.10, 122.47, 122.06, 120.88, 66.10, 62.46, 61.16, 55.74,
BrN2O+6 [M+H]+: 599.0818; found: 599.0873. (Chiralpak column
AD-H, hexane/2-propanol = 70/30, flow rate = 1 mL/min) tR = 26.4
min, 34.1 min.
(20R, 40R, 50S)-Ethyl 20-(1-bromonaphthalen-2-yl)-40-(3-nitrophenyl)-
1,3-dioxo-1,3-dihydrospiro[indene-2,30-pyrrolidine]-50-carboxylate 3g
White sticky oil: Yield = 89% (180 mg); ee = ꢀ76%. 1H NMR
(400 MHz, CDCl3) d 8.08 (s, 1H), 7.89 (d, J = 8.2 Hz, 1H), 7.81 (d, J
= 7.7 Hz, 1H), 7.66 (dd, J = 5.8, 2.9 Hz, 1H), 7.62 (dd, J = 10.9, 4.1
Hz, 1H), 7.54–7.49 (m, 2H), 7.39 (t, J = 6.7 Hz, 1H), 7.25 (dd, J =
8.9, 7.1 Hz, 1H), 6.90 (td, J = 8.3, 1.8 Hz, 1H), 6.72 (td, J = 8.4, 1.9
Hz, 1H), 5.29 (s, 1H), 4.93 (d, J = 10.2 Hz, 1H), 4.30 (d, J = 10.2 Hz,
1H), 4.08 (dd, J = 15.4, 7.2 Hz, 2H), 2.84 (br, 1H), 1.02 (t, J = 7.1
Hz, 3H). 13C NMR (101 MHz, CDCl3) d 197.26, 197.24, 171.83,
147.02, 141.00, 140.82, 135.95, 135.12, 134.98, 134.88, 134.09,
133.88, 129.32 (d, J = 5.6 Hz), 129.23 (d, J = 5.6 Hz), 128.28,
122.74, 122.12, 121.77, 121.70, 110.46 (d, J = 3.6 Hz), 110.25 (d, J
= 3.4 Hz), 102.14, 101.88, 69.16, 61.87, 61.37, 60.70, 55.52, 13.01.
50.90. IR (KBr)
t
.
2924, 1750, 1700, 1590, 1468, 1388, 1255, 1207,
849, 524 cmꢀ1
HRMS Calcd. For C26H19BrCl2NO+4 [M+H]+:
559.9854; found: 559.9871. (Chiralpak column OJ-H, hexane/2-
propanol = 70/30, flow rate = 1 mL/min) tR = 26.3 min, 39.3 min.
(20R, 40R, 50R)-Methyl 40-(4-bromophenyl)-20-(2-chlorophenyl)-1,3-
dioxo-1,3-dihydrospiro[indene-2,30-pyrrolidine]-50-carboxylate 3d
White sticky oil: Yield = 79% (166 mg); ee = ꢀ73.2%. 1H NMR
(400 MHz, CDCl3) d 7.76 (dd, J = 10.1, 5.3 Hz, 1H), 7.63–7.57 (m,
2H), 7.55 (dd, J = 10.0, 5.5 Hz, 1H), 7.47 (dd, J = 16.2, 8.0 Hz, 1H),
7.33 (t, J = 7.8 Hz, 1H), 7.20–7.15 (m, 2H), 7.10 (td, J = 6.4, 1.5 Hz,
2H), 7.06–7.01 (m, 2H), 5.49 (s, 1H), 4.92 (d, J = 10.4 Hz, 1H), 4.21
(d, J = 10.4 Hz, 1H), 3.61 (s, 3H), 2.87 (br, 1H). 13C NMR (101
MHz, CDCl3) d 197.29, 196.59, 171.56, 141.37, 136.88, 134.82,
134.56, 134.49, 134.32, 130.47, 129.50, 129.34, 129.29, 129.12,
127.85, 127.62, 125.99, 125.59, 66.79, 64.21, 62.84, 61.46, 51.33.
IR (KBr)
t 2979, 1736, 1707, 1595, 1525, 1498, 1424, 1348, 1257,
1212, 1100, 845, 797, 587, 565 cmꢀ1. HRMS Calcd. For C27H21F2N2-
O+6 [M+H]+: 507. 1368; found: 507.1377. (Chiralpak column AD-H,
hexane/2-propanol = 70/30, flow rate = 1 mL/min) tR = 18.7 min,
27.7 min.
(20S, 40R, 50R)-Methyl 40-(3-nitrophenyl)- 1,3-dioxo-20-(m-tolyl)-1,3-
dihydrospiro[indene-2,30-pyrrolidine]-50-carboxylate 3h
Yellow crystal: Yield 75% (141 mg); ee = ꢀ76.8%; mp = 68–69
°C. 1H NMR (400 MHz, CDCl3) d 8.08 (s, 1H), 7.89–7.84 (m, 1H),
7.71 (d, J = 7.7 Hz, 1H), 7.55–7.49 (m, 2H), 7.43 (t, J = 7.3 Hz, 1H),
7.37 (d, J = 7.5 Hz, 1H), 7.24 (t, J = 6.0 Hz, 1H), 6.85 (dd, J = 16.4,
6.7 Hz, 3H), 6.75 (dd, J = 10.3, 7.0 Hz, 2H), 4.98 (s, 1H), 4.95 (d, J
= 9.5 Hz, 1H), 4.45 (d, J = 9.5 Hz, 1H), 3.64 (s, 3H), 3.17 (s, 1H),
IR (KBr)
t 2925, 1737, 1702, 1592, 1437, 135, 1327, 1258, 1034,
1010, 756, 633 cmꢀ1. HRMS Calcd. For C26H22BrClNO+4 [M+H]+:
526.0244; found: 526.0243. Calcd. For C26H20N2O+5 [MꢀMeO+H]+:
440.1372; found: 440.1864. (Chiralpak column AS-H, hexane/2-
propanol = 85/15, flow rate = 1 mL/min) tR = 26.2 min, 41.9 min.
2.02 (s, 3H). IR (KBr)
t 2954, 1735, 1698, 1590, 1526, 1348, 1254,
(20R, 40R, 50S)-Methyl 20-(1-bromonaphthalen-2-yl)-40-(4-
1208, 1074, 1051, 872, 778, 698, 684 cmꢀ1. HRMS Calcd. For
bromophenyl)-1,3-dioxo-1,3-dihydrospiro[indene-2,30-pyrrolidine]-
50-carboxylate 3e
C
C
27H23N2O+6 [M+H]+: 471.1556; found: 471.1559. Calcd. For
26H20N2O+5 [MꢀMeO+H]+: 440.1372; found: 440.1864. (Chiralpak
Light yellow sticky oil: Yield = 89% (220 mg); ee = ꢀ80.8%. 1H
NMR (400 MHz, CDCl3) d 8.26 (d, J = 8.6 Hz, 1H), 7.92–7.80 (m,
2H), 7.74–7.61 (m, 2H), 7.58–7.46 (m, 1H), 7.44 (d, J = 5.5 Hz,
3H), 7.38–7.24 (m, 3H), 7.17 (dd, J = 16.7, 7.4 Hz, 1H), 7.12 (d, J =
8.5 Hz, 1H), 7.05 (dd, J = 12.4, 8.5 Hz, 2H), 6.88 (d, J = 8.5 Hz, 1H),
5.80 (s, 1H), 5.02 (d, J = 10.6 Hz, 1H), 4.21 (d, J = 10.6 Hz, 1H),
3.58 (s, 3H), 3.16 (br, 1H). 13C NMR (101 MHz, CDCl3) d 201.06,
196.51, 171.48, 141.74, 140.03, 137.10, 134.73, 134.53, 133.19,
131.17, 130.54, 130.44, 130.31, 129.51, 129.34, 127.26, 126.54,
126.47, 126.35, 126.17, 125.95, 125.49, 122.26, 121.89, 121.85,
AD-H column, hexane/2-propanol = 85/15, flow rate = 0.8 mL/
min) tR = 59.3 (minor), 60.5 (minor), 72.5 (major) and 74.1 (major).
(20S, 40R, 50R)-Methyl 40-(3-nitrophenyl)-1,3-dioxo-20-(o-tolyl)-1,3-
dihydrospiro[indene-2,30-pyrrolidine]-50-carboxylate 3i
Ligh yellow crystal: Yield = 76% (142 mg); ee = ꢀ72%; mp = 73–
74 °C. 1H NMR (400 MHz, CDCl3) d 8.12 (s, 1H), 7.90 (dd, J = 8.1, 1.1
Hz, 1H), 7.71 (d, J = 7.5 Hz, 1H), 7.58–7.50 (m, 2H), 7.49–7.39 (m,
3H), 7.27 (t, J = 8.0 Hz, 1H), 6.95 (d, J = 7.7 Hz, 1H), 6.85 (t, J = 7.3
Hz, 1H), 6.73 (d, J = 7.5 Hz, 1H). 5.33 (s, 1H), 5.01 (d, J = 9.6 Hz,
1H), 4.50 (d, J = 9.6 Hz, 1H), 3.66 (s, 3H), 3.06 (br, 1H), 2.03 (s,
3H). 13C NMR (101 MHz, CDCl3) d 198.34, 197.74, 172.80, 147.11,
141.45, 140.67, 136.40, 134.96, 134.86, 134.54, 132.57, 129.51,
120.87, 67.03, 65.80, 61.55, 54.24, 51.30. IR (KBr)
t 2954, 1733,
1699, 1591, 1495, 1388, 1330, 1254, 1214, 750, 529 cmꢀ1. HRMS
Calcd. For C30H22Br2NO+4 [M+H]+: 619.9895; found: 619.9917. (Chi-