65% ee (Chiralcel AD-H, i-propanol/hexane = 20/80, flow rate
1.0 mL min-1, l = 254 nm); tr = 9.77 and 13.32 min.
7.33–7.23 (m, 5H), 7.03 (t, J = 7.5 Hz, 1H), 6.86 (m, 4H), 6.69 (t,
J = 7.8 Hz, 1H), 6.56 (d, J = 7.5 Hz, 1H), 6.07 (d, J = 7.5 Hz, 1H),
4.72 (s 1H), 4.63 (d, J = 4.8 Hz, 1H), 4.16 (d, J = 4.5 Hz, 1H),
3.82 (s, 3H), 2.19 (s, 3H),; 13C NMR (CDCl3, TMS, 75 MHz) d
21.34, 52.81, 57.44, 64.27, 66.21, 72.33, 109.68, 122.00, 125.32,
126.54, 127.80, 128.17, 128.79, 129.00, 129.20, 132.60, 137.80,
139.34, 141.42, 173.27, 180.32; IR (KBr) n 3683, 3619, 3437,
3019, 2976, 2400, 1738 cm-1. HRMS calcd. for C26H24N2O3+H+:
413.1860 found 413.1857. The product was analyzed by HPLC
to determine the enantiomeric excess: 59% ee (Chiralcel AD-H,
i-propanol/hexane = 20/80, flow rate 1.0 mL min-1, l = 254 nm);
tr = 11.41 and 17.69 min.
(2¢R,3¢S,4¢R,5¢R)-methyl 2¢-(4-bromophenyl)-2-oxo-4¢-phenyl-
spiro[indoline-3,3¢-pyrrolidine]-5¢-carboxylate (6ad). The title
compound was prepared according to the general procedure as
◦
described above in 86% yield. m.p. 152–153 C; [a]2D5 = +71.4 (c
1.20, CHCl3);1H NMR (CDCl3, TMS, 300 MHz) d 7.97 (s, 1H),
7.34–7.20 (m, 7H), 7.05 (t, J = 7.2 Hz, 1H), 6.84 (d, J = 8.7 Hz,
2H), 6.69 (t, J = 7.8 Hz, 1H), 6.10 (d, J = 7.5 Hz, 1H), 6.01 (d,
J = 7.5 Hz, 1H), 4.72 (s, 1H), 4.64 (d, J = 4.8 Hz, 1H), 4.16 (d,
J = 4.5 Hz, 1H), 3.82 (s, 3H);13C NMR (CDCl3, TMS, 75 MHz) d
52.83, 57.01, 64.16, 66.10, 71.76, 109.87, 122.18, 122.21, 125.25,
127.47, 127.89, 128.43, 128.49, 128.82, 129.12, 131.32, 135.13,
138.97, 141.34, 173.42, 180.05; IR (KBr) n 3684, 3621, 3436, 3019,
2976, 2400, 1713 cm-1. HRMS calcd. for C25H21BrN2O3+H+:
477.0808 found 477.0800. The product was analyzed by HPLC
to determine the enantiomeric excess: 59% ee (Chiralcel AD-H,
i-propanol/hexane = 20/80, flow rate 1.0 mL min-1, l = 254 nm);
tr = 12.76 and 17.87 min.
(2¢R,3¢S,4¢R,5¢R)-methyl
[indoline-3,3¢-pyrro-lidine]-5¢-carboxylate
2¢-cyclohexyl-2-oxo-4¢-phenylspiro-
(6ah). The title
compound was prepared according to the general procedure as
◦
described above in 92% yield. m.p. 178–179 C; [a]2D5 = -5.4 (c
0.32, CHCl3);1H NMR (CDCl3, TMS, 300 MHz) d 7.10–6.93
(m, 6H), 6.68–6.60 (m, 2H), 6.22 (d, J = 5.7 Hz, 1H), 4.39 (d,
J = 5.1 Hz, 1H), 3.87 (d, J = 7.5 Hz, 1H), 3.65 (s, 3H), 3.40
(d, J = 8.1 Hz, 1H), 2.07–0.78 (m, 11H); 13C NMR (CDCl3,
TMS, 100 MHz) d 25.92, 26.25, 30.22, 32.01, 39.73, 52.60,
61.16, 62.09, 64.90, 73.74, 109.55, 121.94, 125.27, 127.44, 127.81,
128.31, 128.74, 130.40, 137.90, 172.70, 181.53; HRMS calcd.
for C25H28N2O3+H+: 405.2172 found 405.2171. The product
was analyzed by HPLC to determine the enantiomeric excess:
50% ee (Chiralcel AD-H, i-propanol/hexane = 20/80, flow rate
1.0 mL min-1, l = 254 nm); tr = 6.01 and 13.27 min.
(2¢R,3¢S,4¢R,5¢R)-methyl 2¢-(2-bromophenyl)-2-oxo-4¢-phenyl
spiro[indoline-3,3¢-pyrrolidine]-5¢-carboxylate (6ae). The title
compound was prepared according to the general procedure as
◦
described above in 63% yield. m.p. 160–162 C; [a]2D5 = -12.6 (c
0.86, CHCl3);1H NMR (CDCl3, TMS, 300 MHz) d 8.04 (d, J =
7.8 Hz, 1H), 7.76 (s, 1H), 7.39 (d, J = 7.8 Hz, 2H), 7.16–6.93 (m,
8H), 6.58 (d, J = 7.8 Hz, 1H), 5.38 (s 1H), 4.85 (d, J = 8.1 Hz, 1H),
4.01 (d, J = 8.7 Hz, 1H), 3.75 (s, 3H);13C NMR (CDCl3, TMS,
100 MHz) d 52.77, 56.54, 63.87, 63.94, 68.73, 109.82, 122.29,
124.46, 125.19, 127.76, 127.80, 128.27, 128.53, 128.91, 129.28,
129.83, 129.99, 132.43, 134.91, 138.73, 140.60, 173.67, 177.83; IR
(KBr) n 3618, 3019, 2976, 2399, 1733, 1216 cm-1. HRMS calcd.
for C25H21BrN2O3+H+: 477.0808 found 477.0810,. The product
was analyzed by HPLC to determine the enantiomeric excess:
71% ee (Chiralcel AD-H, i-propanol/hexane = 20/80, flow rate
1.0 mL min-1, l = 254 nm); tr = 10.80 and 13.67 min.
(2¢R,3¢S,4¢R,5¢R)-methyl 2¢,4¢-bis(4-chlorophenyl)-2-oxospiro
[indoline-3,3¢-pyrrolidine]-5¢-carboxylate
(6ba). The
title
compound was prepared according to the general procedure as
◦
described above in 91% yield. m.p. 152–154 C; [a]2D5 = +81.3 (c
0.88, CHCl3);1H NMR (CDCl3, TMS, 300 MHz) d 7.84 (s, 1H),
7.30–7.06 (m, 7H), 6.67 (t, J = 7.8 Hz, 1H), 6.61 (d, J = 7.8 Hz,
1H), 6.18 (d, J = 7.8 Hz, 1H), 4.66 (s 1H), 4.54 (d, J = 5.1 Hz, 1H),
4.10 (d, J = 6.0 Hz, 1H), 3.80 (s, 3H);13C NMR (CDCl3, TMS,
100 MHz) d 51.60, 55.19, 62.83, 64.63, 70.43, 109.77, 121.18,
123.89, 126.14, 126.75, 127.14, 127.41, 127.66, 129.13, 132.35,
132.68, 133.30, 135.94, 140.05, 171.81, 178.61; IR (KBr) n 3684,
3620, 3436, 3019, 2976, 2400, 1734, 1716 cm-1. HRMS calcd.
for C25H20Cl2N2O3+H+: 467.0924 found 467.0914. The product
was analyzed by HPLC to determine the enantiomeric excess:
59% ee (Chiralcel AD-H, i-propanol/hexane = 20/80, flow rate
1.0 mL min-1, l = 254 nm); tr = 11.04 and 13.84 min.
(2¢R,3¢S,4¢R,5¢R)-methyl 2¢-(4-fluorophenyl)-2-oxo-4¢-phenyl-
spiro[indoline-3,3¢-pyrrolidine]-5¢-carboxylate (6af). The title
compound was prepared according to the general procedure as
◦
described above in 80% yield. m.p. 89–90 C; [a]2D5 = +67.9 (c
1.12, CHCl3);1H NMR (CDCl3, TMS, 300 MHz) d 8.53 (s, 1H),
7.24–7.13 (m, 5H), 6.96 (t, J = 7.5 Hz, 1H), 6.86–6.82 (m, 2H),
6.65–6.58 (m, 3H), 6.52 (d, J = 7.5 Hz, 1H), 5.95 (d, J = 7.2 Hz,
1H), 4.62 (s, 1H), 4.52 (d, J = 4.8 Hz, 1H), 4.06 (d, J = 4.5 Hz,
1H), 3.72 (s, 3H);13C NMR (CDCl3, TMS, 75 MHz) d 52.30,
56.72, 63.80, 65.71, 71.43, 76.41, 109.22, 114.53, 114.81, 121.70,
124.85, 127.10, 127.37, 127.81, 127.91, 128.35, 128.65, 131.08,
138.68, 140.90, 160.49, 163.76, 172.86, 179.68; IR (KBr) n 3683,
3621, 3437, 3019, 2975, 2400, 1734, 1713 cm-1. HRMS calcd.
for C25H21FN2O3+H+:,417.1609 found 417.1603. The product
was analyzed by HPLC to determine the enantiomeric excess:
50% ee (Chiralcel AD-H, i-propanol/hexane = 20/80, flow rate
1.0 mL min-1, l = 254 nm); tr = 10.33 and 12.67 min.
(2¢R,3¢S,4¢R,5¢R)-methyl
4¢-(4-bromophenyl)-2¢-(4-chloro-
phenyl)-2-oxospiro[indoline-3,3¢-pyrrolidine]-5¢-carboxylate (6ca).
The title compound was prepared according to the general
procedure as described above in 75% yield. m.p. 159–160 ◦C;
[a]2D5 = +183.2 (c 0.78, CHCl3);1H NMR (CDCl3, TMS, 300 MHz)
d 8.04 (s, 1H), 7.42 (d, J = 7.5 Hz, 2H), 7.10–7.05 (m, 5H), 6.98
(d, J = 7.2 Hz, 2H), 6.78 (t, J = 7.5 Hz, 1H), 6.61 (d, J = 8.1 Hz,
1H), 6.21 (d, J = 7.2 Hz, 1H), 4.68 (s, 1H), 4.55 (d, J = 5.7 Hz,
1H), 4.10 (d, J = 5.1 Hz, 1H), 3.81 (s, 3H);13C NMR (CDCl3,
TMS, 75 MHz) d 51.59, 55.27, 62.78, 64.55, 70.43, 108.79,
120.50, 123.88, 126.16, 126.75, 127.13, 127.41, 129.48, 130.59,
132.66, 133.34, 136.44, 140.06, 171.82, 178.61; IR (KBr) n 3683,
3620, 3437, 3018, 2976, 2400, 1733, 1716 cm-1. HRMS calcd.
for C25H20BrClN2O3+H+: 511.0419 found 511.0415. The product
(2¢R,3¢S,4¢R,5¢R)-methyl
[indoline-3,3¢-pyrroli-dine]-5¢-carboxylate
2-oxo-4¢-phenyl-2¢-p-tolylspiro-
(6ag). The title
compound was prepared according to the general procedure as
◦
described above in 81% yield. m.p. 143–144 C; [a]2D5 = +72.8 (c
1.20, CHCl3);1H NMR (CDCl3, TMS, 300 MHz) d 8.45 (s, 1H),
1984 | Org. Biomol. Chem., 2011, 9, 1980–1986
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