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C. Joie et al.
PAPER
IR (ATR): 3363, 2898, 1702, 1596, 1494, 1447, 1373, 1304, 1245,
1175, 1116, 1034, 981, 927, 869, 785, 749, 693 cm–1.
13C NMR (150 MHz, DMSO-d6): δ = 14.4 (CH3), 28.0 [3 C,
C(CH3)3], 56.2 (NCHCH), 57.4 (NCHPh), 60.4 (CH2), 80.5 (COH),
84.7 [C(CH3)3], 115.6 (CHAr), 116.7 (C), 120.0 (CHAr), 123.4
(CHAr), 124.2 (2 C, CHAr), 124.9 (CHAr), 125.5 (CHCOOEt), 125.9
(CHAr), 126.1 (CHAr), 126.7 (2 C, CHAr), 126.9 (C), 127.9 (CHAr),
128.4 (2 C, CHAr), 128.6 (2 C, CHAr), 135.4 (C), 137.8 (C), 141.6
(C), 142.2 (CH=CHCOOEt), 149.2 (COOt-Bu), 165.2 (COOEt),
172.9 (NCO).
1H NMR (600 MHz, CDCl3): δ = 1.26 (t, J = 7.2 Hz, 3 H, CH3),
2.91 (t, J = 8.4 Hz, 1 H, NCHCH), 3.22 (br s, 1 H, OH), 4.15 (q,
J = 7.2 Hz, 2 H, CH2), 5.16 (d, J = 8.4 Hz, 1 H, NCHPh), 5.41 (d,
J = 16.2 Hz, 1 H, CHCOOEt), 5.89 (s, 2 H, CH2), 6.62 (s, 1 H,
CHAr), 6.65 (s, 2 H, CHAr), 7.13 (t, J = 7.8 Hz, 1 H, CHAr), 7.19 (dd,
J = 9.0, 16.2 Hz, 1 H, CH=CHCOOEt), 7.26–7.47 (m, 9 H, CHAr).
MS (EI, 70 eV): m/z (%) = 566 (43), 466 (29), 449 (23), 448 (100),
249 (21), 220 (16).
HRMS: m/z [M + H]+ calcd for C34H35N2O6: 567.2489; found:
567.2488.
13C NMR (150 MHz, CDCl3): δ = 14.2 (CH3), 59.7 (NCHCH), 60.5
(CH2), 65.0 (NCHPh), 80.8 (COH), 101.2 (CH2), 106.7 (CHAr),
108.3 (CHAr), 121.4 (CHAr), 123.9 (2 C, CHAr), 125.8 (2 C, CHAr),
126.0 (CHAr), 126.5 (CHCOOEt), 128.2 (CHAr), 128.5 (2 C, CHAr),
128.7 (2 C, CHAr), 130.9 (C), 136.9 (C), 139.6 (CHCOOEt), 140.5
(C), 147.5 (C), 148.2 (C), 165.5 (COOEt), 173.7 (NCO).
Ethyl (E)-3-[(2S,3R,4R)-4-Hydroxy-1-(2-iodophenyl)-5-oxo-
2,4-diphenylpyrrolidin-3-yl]acrylate (6j)
MS (EI, 70 eV): m/z (%) = 471 (25), 454 (19), 453 (59), 380 (18),
379 (27), 246 (28), 226 (100), 225 (92), 224 (55), 201 (38), 172
(47), 144 (27), 135 (81), 115 (35), 105 (96), 77 (44).
HRMS: m/z [M + H]+ calcd for C28H26NO6: 422.1755; found:
Following the general procedure with purification by flash chroma-
tography (n-pentane–EtOAc, 3:1) gave 6j as a colorless solid; yield:
80 mg (44%); mp 92–95 °C; 88% ee (95%) [chiral stationary phase
HPLC (Daicel AS)]; Rf = 0.28 (n-pentane–EtOAc, 3:1); [α]D22 +4.0
(c 1.0, CHCl3).
472.1757.
IR (ATR): 3366, 2980, 2176, 2113, 1707, 1581, 1470, 1373, 1306,
1252, 1174, 1119, 1029, 980, 913, 869, 803, 748, 699 cm–1.
Ethyl (E)-3-[(2S,3R,4R)-2-(Furan-2-yl)-4-hydroxy-5-oxo-1,4-
diphenylpyrrolidin-3-yl]acrylate (6h)
Following the general procedure with purification by flash chroma-
tography (n-pentane–EtOAc, 3:1) gave 6h as a colorless solid;
yield: 70 mg (51%); mp 62–65 °C; 60% ee [chiral stationary phase
HPLC (Daicel AS)]; Rf = 0.35 (n-pentane–EtOAc, 3:1); [α]D
+32.7 (c 0.49, CHCl3).
1H NMR (600 MHz, DMSO-d6): δ = 1.11 (t, J = 7.2 Hz, 3 H, CH3),
3.19 (t, J = 8.4 Hz, 1 H, NCHCH), 4.00 (q, J = 7.2 Hz, 2 H, CH2),
5.39 (d, J = 15.6 Hz, 1 H, CHCOOEt), 5.54 (d, J = 9.6 Hz, 1 H,
NCHPh), 6.91 (m, 2 H, CHAr), 7.00 (dd, J = 9.0, 15.6 Hz, 1 H,
CH=CHCOOEt), 7.16 (m, 1 H, CHAr), 7.22 (m, 3 H, CHAr), 7.32 (m,
2 H, CHAr), 7.41 (m, 2 H, CHAr), 7.47 (m, 2 H, CHAr), 7.58 (m, 2 H,
CHAr), 7.77 (d, J = 7.8 Hz, 1 H, CHAr).
13C NMR (150 MHz, DMSO-d6): δ = 14.4 (CH3), 59.5 (NCHCH),
60.5 (CH2), 65.3 (NCHPh), 80.1 (COH), 100.1 (C), 125.4 (CH-
COOEt), 126.7 (2 C, CHAr), 126.9 (CHAr), 127.9 (CHAr), 128.3 (2
C, CHAr), 128.7 (2 C, CHAr), 128.8 (CHAr), 128.9 (2 C, CHAr), 129.1
(CHAr), 129.2 (CHAr), 137.6 (C), 139.8 (CHAr), 140.8 (C), 141.7
(CH=CHCOOEt), 141.9 (C), 165.2 (COOEt), 171.8 (NCO).
22
IR (ATR): 3358, 3063, 2982, 1697, 1596, 1547, 1495, 1448, 1375,
1304, 1247, 1175, 1122, 1070, 1015, 979, 923, 880, 839, 743, 693
cm–1.
1H NMR (600 MHz, CDCl3): δ = 1.24 (t, J = 7.2 Hz, 3 H, CH3),
3.39 (t, J = 8.4 Hz, 1 H, NCHCH), 3.54 (br s, 1 H, OH), 4.14 (q,
J = 7.2 Hz, 2 H, CH2), 5.21 (d, J = 8.4 Hz, 1 H, NCHPh), 5.55 (d,
J = 16.2 Hz, 1 H, CHCOOEt), 6.19–6.22 (m, 2 H, CHAr), 7.13 (dd,
J = 8.4, 16.2 Hz, 1 H, CH=CHCOOEt), 7.18–7.21 (m, 3 H, CHAr),
7.29–7.47 (m, 8 H, CHAr).
13C NMR (150 MHz, CDCl3): δ = 14.1 (CH3), 54.8 (NCHCH), 59.4
(NCHPh), 60.5 (CH2), 80.3 (COH), 110.4 (CHAr), 111.4 (CHAr),
124.9 (2 C, CHAr), 125.9 (2 C, CHAr), 126.1 (CHCOOEt), 126.9
(CHAr), 128.2 (CHAr), 128.4 (2 C, CHAr), 128.8 (2 C, CHAr), 136.7
(C), 139.8 (CH=CHCOOEt), 140.3 (C), 143.2 (CHAr), 148.6 (C),
165.5 (COOEt), 173.3 (NCO).
MS (EI, 70 eV): m/z (%) = 553 (6), 536 (13), 427 (26), 426 (92), 424
(17), 308 (30), 224 (33), 203 (19), 202 (30), 180 (17), 157 (27), 144
(10), 129 (28), 128 (16), 105 (100), 77 (31).
Anal. Calcd for C27H24INO4: C, 58.60; H, 4.37; N, 2.53. Found: C,
58.59; H, 4.09; N, 2.37.
Ethyl (E)-3-[(2S,3R,4R)-4-Hydroxy-1-(4-methoxyphenyl)-5-
oxo-2,4-diphenylpyrrolidin-3-yl]acrylate (6k)
MS (EI, 70 eV): m/z (%) = 419 (18), 418 (32), 417 (23), 401 (27),
400 (100), 399 (85), 354 (12), 353 (10), 324 (17), 301 (22), 299
(13), 193 (23), 192 (51), 191 (33), 173 (25), 172 (31), 171 (21), 170
(11).
Following the general procedure with purification by flash chroma-
tography (n-pentane–EtOAc, 3:1) gave 6k as a colorless solid;
yield: 86 mg (60%); mp 77–79 °C; 81% ee (89%) [chiral stationary
phase HPLC (Daicel AS)]; Rf = 0.21 (n-pentane–EtOAc, 3:1);
[α]D22 +102.0 (c 0.5, CHCl3).
HRMS: m/z [M + H]+ calcd for C25H24NO5: 418.1649; found:
418.1650.
IR (ATR): 3356, 2974, 1695, 1510, 1453, 1375, 1293, 1243, 1173,
1114, 1030, 981, 832, 795, 751, 697 cm–1.
tert-Butyl 3-{(2S,3R,4R)-3-[(E)-3-Ethoxy-3-oxoprop-1-enyl]-4-
hydroxy-5-oxo-1,4-diphenylpyrrolidin-2-yl}-1H-indole-1-car-
boxylate (6i)
Following the general procedure with purification by flash chroma-
tography (n-pentane–EtOAc, 3:1) gave 6i as a colorless solid; yield:
110 mg (59%); mp 110–115 °C; 81% ee (88%) [chiral stationary
1H NMR (600 MHz, CDCl3): δ = 1.24 (t, J = 7.2 Hz, 3 H, CH3),
2.95 (t, J = 8.4 Hz, 1 H, NCHCH), 3.34 (br s, 1 H, OH), 3.72 (s, 3
H, OCH3), 4.14 (q, J = 7.2 Hz, 2 H, CH2), 5.18 (d, J = 8.4 Hz, 1 H,
NCHPh), 5.37 (d, J = 15.6 Hz, 1 H, CHCOOEt), 6.76 (d, J = 9.0 Hz,
2 H, CHAr), 7.16–7.40 (m, 11 H, CHAr, CH=CHCOOEt), 7.47 (d,
J = 7.8 Hz, 2 H, CHAr).
13C NMR (150 MHz, CDCl3): δ = 14.1 (CH3), 55.3 (OCH3), 59.6
(NCHCH), 60.5 (CH2), 65.6 (NCHPh), 80.8 (COH), 114.0 (2 C,
CHAr), 125.4 (2 C, CHAr), 125.8 (2 C, CHAr), 126.3 (CHCOOEt),
127.3 (2 C, CHAr), 128.2 (CHAr), 128.3 (CHAr), 128.5 (2 C, CHAr),
128.8 (2 C, CHAr), 129.9 (C), 137.2 (C), 139.8 (CH=CHCOOEt),
140.7 (C), 157.5 (C), 165.5 (COOEt), 173.8 (NCO).
22
phase HPLC (Daicel AS)]; Rf = 0.4 (n-pentane–EtOAc, 3:1); [α]D
+68.2 (c 0.51, CHCl3).
IR (ATR): 3379, 2980, 1710, 1602, 1456, 1364, 1253, 1154, 1084,
1032, 981, 849, 749, 696 cm–1.
1H NMR (600 MHz, C6D6): δ = 1.23 (t, J = 7.2 Hz, 3 H, CH3), 1.64
(s, 9 H, CH3), 3.78 (t, J = 8.4 Hz, 1 H, NCHCH), 4.13 (br s, 1 H,
OH), 4.13 (q, J = 7.2 Hz, 2 H, CH2), 5.40 (d, J = 15.6 Hz, 1 H, CH-
COOEt), 5.43 (d, J = 8.4 Hz, 1 H, NCHPh), 7.10 (t, 1 H, CHAr),
7.18–7.27 (m, 5 H, CHAr), 7.38–7.42 (m, 5 H, CHAr), 7.47 (br s, 1
H, CHAr), 7.51 (d, J = 7.2 Hz, 2 H, CHAr), 7.57 (d, J = 7.8 Hz, 1 H,
CHAr), 8.02 (br s, 1 H, CHAr).
MS (EI, 70 eV): m/z (%) = 458 (17), 457 (100), 456 (36), 340 (12),
256 (16), 255 (16), 213 (12), 212 (36), 211 (34), 210 (14), 197 (15),
196 (17).
Synthesis 2014, 46, 799–808
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