K. Ding, J. Meng et al.
FULL PAPER
ic filtrate was then concentrated to dryness under reduced pressure. The
crude product was purified as outlined in the following paragraphs.
831, 814, 735, 696, 681 cmÀ1
;
ESI-MS [M+H+]: 1981.9; HRMS
(MALDI): calcd for C132H110O17N [M+H+] 1980.7768; found: 1980.7735.
10a: Reaction of (S)-NOBIN with 8a and purification of the product by
recrystallization from CH2Cl2/hexane gave 10a as a red crystalline solid
in 95.5% yield. M.p. 112 1148C; [a]2D0 = À66.08 (c = 0.25, CHCl3); 1H
NMR (300 MHz, CDCl3, TMS): d = 11.57 (s, 1H; OH), 8.64 (s, 1H;
CH=N), 8.12(d, J = 9.0 Hz, 1H; ArH), 7.97 (d, J = 8.4 Hz, 2H; ArH),
7.88 (d, J = 7.8 Hz, 1H; ArH), 7.67 (d, J = 9.0 Hz, 1H; ArH), 7.54 7.49
(m, 1H; ArH), 7.41 7.18 (m, 10H; ArH), 7.01 (d, J = 8.1 Hz, 1H; ArH),
6.99 6.83 (m, 2H; ArH), 6.70 (d, J = 8.7 Hz, 1H; ArH), 4.98 ppm (s,
2H; PhCH2O); 13C NMR (75 MHz, CDCl3): d = 162.26, 155.68, 151.35,
151.17, 145.21, 137.19, 133.86, 133.71, 133.03, 130.97, 130.57, 129.32,
128.83, 128.56, 128.53, 128.23, 127.82, 127.69, 126.95, 126.65, 126.63,
125.83, 124.75, 123.67, 121.82, 118.99, 118.39, 117.80, 117.64, 116.95,
116.04, 71.14 ppm; IR (KBr): n˜ = 3328, 3053, 2926, 2830, 1625, 1575,
1516, 1490, 1454, 1436, 1280, 1344, 1274, 1209, 1151, 1042, 1024, 979, 945,
927, 861, 808, 787, 747, 734, 695 cmÀ1; ESI-MS [M+Na+] 518.3; HRMS
(MALDI): calcd for C34H26O3 [M+H+] 496.1907; found: 496.1902.
9a: Reaction of (S)-NOBIN with 7a and purification of the product by
recrystallization from CH2Cl2/hexane (1:5) gave 9a as a yellow crystalline
solid in 99% yield; m.p. 114 1168C; [a]2D0 = À207.68 (c = 0.33, CHCl3);
1H NMR (300 MHz, CDCl3, TMS): d = 12.55 (s, 1H; OH), 8.63 (s, 1H;
CH=N), 8.11 (d, J = 8.7 Hz, 1H; ArH), 7.97 (dd, J = 8.1 Hz, J =
6.0 Hz, 2H; ArH), 7.89 (d, J = 7.8 Hz, 1H; ArH), 7.68 (d, J = 8.7 Hz,
1H; ArH), 7.50 (d, J = 4.2Hz, 1H; ArH), 7.40 7.14 (m, 11H; ArH),
7.02(d, J = 8.1 Hz, 1H; ArH), 6.45 (dd, J = 2.4 Hz, J = 6.0 Hz, 1H;
ArH), 6.33 (d, J = 2.1 Hz, 1H; ArH), 4.98 ppm (s, 2H; PhCH2O); 13C
NMR (75 MHz, CDCl3): d
= 164.80, 163.54, 161.04, 151.39, 144.61,
136.41, 133.91, 133.84, 133.78, 132.76, 130.87, 130.48, 129.28, 128.82,
128.51, 128.50, 128.33, 127.81, 127.69, 126.85, 126.54, 126.36, 125.28,
124.80, 123.55, 117.92, 117.67, 115.97, 113.38, 108.12, 102.14, 70.16 ppm;
IR (KBr): n˜ = 3523, 3053, 2928, 2829, 1609, 1589, 1508, 1433, 1346, 1283,
1244, 1218, 1202, 1115, 994, 979, 811, 748, 738, 698 cmÀ1; EI-MS (70 eV):
m/z (%): 495 (88.6) [M+], 268 (100), 91 (50.8), 496 (49.6), 478 (48.9), 239
(16.2), 269 (13.4), 497 (12.3); HRMS (MALDI): calcd. for C34H26O3
[M+H+] 496.1907; found: 496.1897.
10b: Reaction of (S)-NOBIN with 8b and purification of the product by
flash chromatography on silica gel with CH2Cl2/hexane/Et3N (4:6:1) as
eluent gave 10b in 98.8% yield as a red glass. [a]2D0 = À52.98 (c = 0.50,
9b: Reaction of (S)-NOBIN with 7b and purification of the product by
flash chromatography on silica gel with CH2Cl2/hexane/Et3N (4:6:1) as
eluent gave 9b in 97.7% yield as a yellow glass. [a]2D0 = À137.58 (c =
1
CHCl3); H NMR (300 MHz, CDCl3, TMS): d = 11.59 (s, 1H; OH), 8.62
(s, 1H; CH=N), 8.12(d, J = 9.0 Hz, 1H; ArH), 7.97 (t, J = 8.4 Hz, 2H;
ArH), 7.87 (d, J = 7.8 Hz, 1H; ArH), 7.67 (d, J = 9.0 Hz, 1H; ArH),
7.55 7.49 (m, 1H; ArH), 7.43 7.27 (m, 14H; ArH), 7.24 7.19 (m, 1H;
ArH), 7.01 (d, J = 8.4 Hz, 1H; ArH), 6.88 (dd, J = 3.0 Hz, J = 9.0 Hz,
1H; ArH), 6.78 (d, J = 3.0 Hz, 1H; ArH), 6.79 (d, J = 9.0 Hz, 1H;
ArH), 6.63 (d, J = 2.7 Hz, 2H; ArH), 6.57 (t, J = 2.4 Hz, 1H; ArH),
0.95, CHCl3); 1H NMR (300 MHz, CDCl3, TMS): d
= 12.51 (s, 1H;
OH), 8.62(s, 1H; CH =N), 8.10 (d, J = 9.0 Hz, 1H; ArH), 7.98 7.93 (m,
2H; ArH), 7.87 (d, J = 8.1 Hz, 1H; ArH), 7.67 (d, J = 9.0 Hz, 1H;
ArH), 7.51 7.12(m, 18H; ArH), 7.01 (d, J = 8.4 Hz, 1H; ArH), 6.55
6.54 (m, 2H; ArH), 6.42 (dd, J = 2.4 Hz, J = 9.0 Hz, 1H; ArH), 6.29 (d,
5.01 (d, J
NMR (75 MHz, CDCl3): d
=
6.9 Hz, 4H; PhCH2O), 4.92ppm (s, 2H; PhCH 2O); 13C
161.78, 160.06, 155.38, 151.23, 150.86,
J
=
2.1 Hz, 1H; ArH), 5.02 (s, 4H; PhCH2O), 4.92ppm (s, 2H;
=
PhCH2O); 13C NMR (75 MHz, CDCl3): d
=
165.16, 163.20, 160.27,
144.71, 139.45, 136.66, 133.57, 133.50, 132.68, 130.40, 130.12, 128.88,
128.49, 128.20, 128.16, 127.92, 127.44, 127.34, 126.55, 126.40, 126.21,
124.41, 123.68, 123.21, 121.37, 118.70, 118.01, 117.74, 117.29, 116.51,
115.90, 106.11, 101.45, 70.60, 69.99 ppm; IR (KBr): n˜ = 3523, 3054, 2923,
2824, 1595, 1577, 1488, 1452, 1375, 1343, 1273, 1210, 1153, 1027, 980, 929,
811, 747, 696 cmÀ1; ESI-MS [M+Na+]: 730.4; HRMS (MALDI): calcd for
C48H38O5N [M+H+] 708.2744; found: 708.2737.
159.99, 151.37, 143.70, 138.54, 136.63, 133.57, 132.37, 130.34, 130.12,
128.89, 128.46, 128.19, 128.14, 127.88, 127.44, 127.26, 126.48, 126.27,
125.94, 125.39, 124.44, 123.15, 118.69, 118.02, 117.84, 117.21, 115.63,
113.02, 107.67, 106.16, 101.91, 101.56, 69.94, 69.58 ppm; IR (KBr): n˜ =
3525, 3052, 2927, 2828, 1606, 1561, 1508, 1452, 1376, 1342, 1294, 1245,
1202, 1148, 1116, 1061, 1026, 977, 833, 812, 747, 696 cmÀ1; ESI-MS
[M+H+]: 708.4; HRMS (MALDI): calcd. for C48H38O5N [M+H+]
708.2744; found: 708.2747.
10c: Reaction of (S)-NOBIN with 8c and purification of the product by
flash chromatography on silica gel with CH2Cl2/hexane/Et3N (4:4:1) as
eluent gave 10c in 96.9% yield as a red glass. [a]2D0 = À35.98 (c = 0.935,
9c: Reaction of (S)-NOBIN with 7c and purification of the product by
flash chromatography on silica gel with CH2Cl2/hexane/Et3N (4:4:1) as
eluent gave 9c in 96.5% yield as a yellow glass. [a]2D0 = À66.18 (c =
0.925, CHCl3); 1H NMR (300 MHz, CDCl3, TMS): d = 12.50 (s, 1H;
OH), 8.60 (s, 1H; CH=N), 8.10 (d, J = 8.7 Hz, 1H; ArH), 7.85 8.00 (m,
2H; ArH), 7.86 (d, J = 7.8 Hz, 1H; ArH), 7.66 (d, J = 9.1 Hz, 1H;
ArH), 7.50 7.02(m, 30H; ArH), 6.67 6.29 (m, 9H; ArH), 5.03 (s, 8H;
PhCH2O), 4.94 (s, 4H; PhCH2O), 4.91 ppm (s, 2H; PhCH2O); 13C NMR
1
CHCl3); H NMR (300 MHz, CDCl3, TMS): d = 11.59 (s, 1H; OH), 8.60
(s, 1H; CH=N), 8.07 (d, J = 9.0 Hz, 1H; ArH), 7.97 7.90 (m, 2H; ArH),
7.84 (d, J = 7.5 Hz, 1H; ArH), 7.63 (d, J = 9.0 Hz, 1H; ArH), 7.53 7.18
(m, 27H; ArH), 6.98 (d, J = 8.7 Hz, 1H; ArH), 6.86 (dd, J = 3.0 Hz,
9.0 Hz, 1H; ArH), 6.77 (d, J = 2.7 Hz, 1H; ArH), 6.67 6.65 (m, 5H;
ArH), 6.59 (d, J = 1.8 Hz, 2H; ArH), 6.53 (t, J = 2.1 Hz, 2H; ArH),
5.00 (s, 8H; PhCH2O), 4.95 (s, 4H; PhCH2O), 4.90 ppm (s, 2H;
(75 MHz, CDCl3): d
= 159.88, 139.05, 138.58, 136.65, 135.20, 133.57,
PhCH2O); 13C NMR (75 MHz, CDCl3): d
= 160.06, 155.35, 150.92,
133.44, 132.34, 130.11, 129.95, 129.27, 128.74, 128.45, 128.15, 128.09,
127.86, 127.44, 127.10, 127.02, 126.76, 126.39, 125.84, 124.41, 123.68,
123.41, 123.00, 122.49, 118.09, 117.95, 117.12, 115.91, 113.14, 108.65,
107.52, 106.24, 106.13, 101.81, 101.57, 101.46, 69.91, 69.78, 69.57 ppm; IR
(KBr): n˜ = 3524, 3052, 2924, 2826, 1595, 1508, 1498, 1452, 1375, 1342,
144.73, 139.48, 139.12, 136.66, 133.53, 133.40, 132.69, 130.55, 130.19,
128.93, 128.51, 128.20, 127.93, 127.51, 127.41, 127.19, 126.86, 126.59,
126.32, 126.28, 125.88, 124.42, 123.65, 123.55, 123.29, 121.31, 118.69,
118.00, 117.57, 117.22, 116.72, 116.55, 115.79, 106.26, 106.03, 101.44, 70.56,
69.99, 69.85 ppm; IR (KBr): n˜ = 3525, 3051, 2924, 2827, 1595, 1488, 1452,
1375, 1295, 1272, 1210, 1154, 1052, 1028, 929, 812, 736, 696 cmÀ1; ESI-MS
[M+H+]: 1132.4; HRMS (MALDI): calcd for C76H62O9N [M+H+]
1132.4419; found: 1132.4430.
1295, 1245, 1203, 1154, 1116, 1054, 1028, 978, 832, 813, 736, 696 cmÀ1
;
ESI-MS [M+H+]: 1132.4; HRMS (MALDI): calcd for C76H62O9N
[M+H+] 1132.4419; found: 1132.4407.
9d: Reaction of (S)-NOBIN with 7d and purification of the product by
flash chromatography on silica gel with CH2Cl2/hexane/Et3N (4:4:1) as
eluent gave 9d in 99.0% yield as a yellow glass. [a]2D0 = À36.68 (c =
10d: Reaction of (S)-NOBIN with 8d and purification of the product by
flash chromatography on silica gel with CH2Cl2/hexane/Et3N (4:4:1) as
eluent gave 10d in 96.3% yield as a red glass. [a]2D0 = À21.78 (c = 1.07,
0.94, CHCl3); 1H NMR (300 MHz, CDCl3, TMS): d
= 12.49 (s, 1H;
1
CHCl3); H NMR (300 MHz, CDCl3, TMS): d = 11.58 (s, 1H; OH), 8.55
OH), 8.54 (s, 1H; CH=N), 8.06 7.81 (m, 4H; ArH), 7.61 (d, J = 9.0 Hz,
1H; ArH), 7.42 7.27 (m, 47H; ArH), 7.09 6.98 (m, 2H; ArH), 6.68 6.52
(m, 20H; ArH), 6.41 6.26 (m, 2H; ArH), 5.01 (s, 16H; PhCH2O), 4.94 (s,
8H; PhCH2O), 4.93 (s, 4H; PhCH2O), 4.88 ppm (s, 2H; PhCH2O); 13C
(s, 1H; CH=N), 8.06 (d, J = 9.0 Hz, 1H; ArH), 7.96 7.89 (m, 2H; ArH),
7.85 (d, J = 7.6 Hz, 1H; ArH), 7.62(d, J = 8.9 Hz, 1H; ArH), 7.41 7.26
(m, 47H; ArH), 7.02(d, J = 8.8 Hz, 1H; ArH), 6.66 6.54 (m, 23H;
ArH), 4.99 (s, 16H; PhCH2O), 4.95 (s, 4H; PhCH2O), 4.94 (s, 8H;
PhCH2O), 4.92ppm (s, 2H; PhCH 2O); 13C NMR (75 MHz, CDCl3): d =
161.65, 159.98, 159.88, 157.70, 155.26, 151.00, 150.74, 144.57, 139.48,
139.09, 139.06, 136.97, 136.61, 133.46, 133.36, 132.63, 130.46, 130.14,
128.85, 128.47, 128.33, 128.16, 127.90, 127.70, 127.57, 127.47, 127.34,
127.04, 126.54, 126.29, 126.21, 125.93, 124.38, 123.24, 121.13, 118.65,
117.90, 117.59, 117.07, 116.50, 115.82, 106.26, 105.90, 101.41, 70.37, 69.90,
69.78 ppm; IR (KBr): n˜ = 3526, 3032, 2927, 2871, 1595, 1497, 1451, 1374,
NMR (75 MHz, CDCl3): d
= 160.06, 160.04, 159.97, 159.93, 151.02,
144.51, 139.14, 139.10, 138.66, 136.67, 133.59, 133.50, 133.43, 132.43,
130.52, 130.13, 128.93, 128.58, 128.51, 128.45, 128.40, 128.33, 128.24,
128.17, 127.93, 127.85, 127.73, 127.56, 127.50, 127.43, 127.37, 126.52,
126.22, 126.04, 125.10, 124.45, 123.25, 117.57, 117.20, 115.79, 113.18,
106.30, 106.08, 101.48, 69.98, 69.85, 69.59 ppm; IR (KBr): n˜ = 3525, 3032,
2924, 2854, 1595, 1508, 1498, 1451, 1375, 1342, 1295, 1203, 1153, 1051,
5994
¹ 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2003, 9, 5989 5996