Antibacterial Agents
4296±4310
Compound 61: Rf 0.69 (silica gel, EtOAc/hexanes 1:1); IR (film): nÄmax
J 6.8 Hz, 2H), 2.34 (s, 6H); 13C NMR (100 MHz, [D6]DMSO): d 163.1,
162.2 (d, J 305.2 Hz), 150.7, 142.7, 142.0, 141.3, 129.8, 128.3, 111.7 (d, J
305.2 Hz), 102.0 (t, J 30.3 Hz), 36.9, 28.8, 21.7, 21.0; HRMS (MALDI-
3278, 1659, 1528, 1479, 1011, 812 cm 1; 1H NMR (400 MHz, CD3OD): d
7.49 (d, J 8.5 Hz, 2H), 7.35 (d, J 8.5 Hz, 2H), 7.30 (d, J 8.8 Hz, 2H),
7.17 (d, J 8.2 Hz, 2H), 3.84 (s, 2H), 3.50 (t, J 6.4 Hz, 2H), 2.86 (t, J
6.7 Hz, 2H); 13C NMR (100 MHz, [D6]DMSO): d 163.7, 160.1, 152.2,
151.8, 132.6, 131.3, 131.0, 130.4, 128.8, 116.8, 38.4, 37.4, 28.3; HRMS
FTMS): calcd for C19H20F2N2O2S2 [MNa] : 433.0832, found: 433.0891.
Compound 70: Rf 0.65 (silica gel, EtOAc/hexanes 1:1); IR (film): nÄmax
1
3410, 1658, 1466, 1205, 1009 cm 1; H NMR (400 MHz, CD3OD): d 7.81
(m, 1H), 7.23 (brs, 1H), 7.11 (dm, J 7.9 Hz, 1H), 7.04 (dm, J 7.7 Hz, 1H),
6.88 ± 6.97 (m, 4H), 3.67 (s, 2H), 3.35 (q, J 6.2 Hz, 2H), 2.62 (t, J 7.0 Hz,
2H), 2.34 (s, 6H); 13C NMR (100 MHz, [D6]DMSO): d 163.1, 151.2, 142.0,
139.6, 131.3, 130.5, 129.4, 129.0, 128.5, 128.2, 127.8, 121.5, 36.8, 28.7, 21.7,
(MALDI-FTMS): calcd for C17H16BrClN2O2S2 [MH] : 458.9525, found:
458.9599.
Compound 62: Rf 0.39 (silica gel, EtOAc/hexanes 1:1); 1H NMR
(400 MHz, CD3OD): d 7.91 (s, 1H), 7.73 ± 7.68 (m, 2H), 7.50 (dd, J 8.5,
1.7 Hz, 1H), 7.39 ± 7.35 (m, 2H), 7.08 (d, J 2.1 Hz, 1H), 6.90 (dd, J 8.5,
2.3 Hz, 1H), 6.64 (d, J 8.2 Hz, 2H), 3.63 (s, 2H), 3.45 (t, J 6.7 Hz, 2H),
2.81 (t, J 6.7 Hz, 2H); 13C NMR (100 MHz, [D6]DMSO): d 160.8, 150.6,
142.3, 132.8, 131.5, 130.9, 129.7, 128.5, 125.3, 125.0, 124.2, 124.0, 123.0, 120.9,
120.8, 120.0, 40.9, 38.6, 30.3; HRMS (MALDI-FTMS): calcd for
21.0; HRMS (MALDI-FTMS): calcd for C19H21BrN2O2S2 [MH] :
453.0228, found: 453.0286.
Compound 71: Rf 0.79 (silica gel, EtOAc/hexanes 1:1); 1H NMR
(400 MHz, CD3OD): d 7.43 ± 7.40 (m, 2H), 7.22 ± 7.18 (m, 5H), 7.09 ± 7.06
(m, 2H), 6.93 ± 6.90 (m, 2H), 6.81 ± 6.77 (m, 2H), 5.12 (s, 2H), 3.73 (m, 2H),
3.41 (t, J 7.0 Hz, 2H), 2.74 (t, J 7.0 Hz, 2H); 13C NMR (125 MHz,
[D6]DMSO): d 162.3, 161.7 (d, J 243 Hz), 160.7 (d, J 240 Hz), 159.8,
152.3 (d, J 4.7 Hz), 136.9 (d, J 1.9 Hz), 132.1 (d, J 2.8 Hz), 130.8 (d,
J 8.5 Hz), 130.6 (d, J 7.6 Hz), 128.3 (d, J 3.8 Hz), 128.0 (d, J 5.7 Hz),
116.6 (d, J 21.9 Hz), 116.3 (d, J 21.9 Hz), 115.0 (d, J 20.9 Hz), 76.4,
38.2, 36.7, 29.1; HRMS (MALDI-FTMS): calcd for C24H22F2N2O2S2
C21H19ClN2O3S2 [MH] : 447.0526, found: 447.0614.
Compound 63: Rf 0.41 (silica gel, EtOAc/hexanes 1:1); IR (film): nÄmax
3392, 1664, 1523, 1442, 1225, 1133, 1018, 949, 886, 779, 737 cm 1; 1H NMR
(400 MHz, CD3OD): d 7.24 (d, J 2.0 Hz, 1H), 7.13 (m, 1H), 6.98 (dm,
J 7.6 Hz, 1H), 6.90 (dt, J 10.2, 2.1 Hz, 1H), 6.78 (td, J 8.5, 2.6 Hz, 1H),
6.37 (d, J 1.7 Hz, 1H), 3.82 (s, 2H), 3.48 (t, J 6.7 Hz, 2H), 2.73 (t, J
7.3 Hz, 2H); 13C NMR (100 MHz, [D6]DMSO): d 163.2, 162.1 (d, J
240 Hz), 151.2 (d, J 7.8 Hz), 141.8, 139.5, 130.1, 124.8, 115.4 (d, J
20.9 Hz), 114.5, 112.9 (d, J 20.9 Hz), 112.4, 38.0, 36.4, 28.7, 11.6; HRMS
[MH] : 473.1091, found: 473.1163.
Compound 72: Rf 0.72 (silica gel, EtOAc/hexanes 1:1); IR (film): nÄmax
3411, 1670, 1611, 1431, 1223, 1046, 825 cm 1; 1H NMR (400 MHz, CD3OD):
d 7.47 ± 7.43 (m, 2H), 7.13 ± 7.10 (m, 2H), 6.98 ± 6.94 (m, 2H), 6.84 ± 6.81
(m, 2H), 3.90 (s, 3H), 3.76 (s, 2H), 3.42 (t, J 6.7 Hz, 2H), 2.75 (t, J
6.4 Hz, 2H); 13C NMR (125 MHz, [D6]DMSO): d 162.3, 162.1 (d, J
243 Hz), 161.3 (d, J 240 Hz), 159.8, 151.9, 132.1 (d, J 1.9 Hz), 130.8 (d,
J 8.5 Hz), 130.6 (d, J 8.5 Hz), 130.5 (d, J 8.5 Hz), 116.6 (d, J
21.9 Hz), 116.3 (d, J 21.9 Hz), 115.1 (d, J 20.9 Hz), 62.6, 38.1, 36.6,
(MALDI-FTMS): calcd for C16H17FN2O3S2 [MNa] : 391.0562, found:
391.0560.
Compound 64: Rf 0.66 (silica gel, EtOAc/hexanes 1:1); 1H NMR
(400 MHz, CD3OD): d 8.73 (dd, J 4.4, 1.7 Hz, 1H), 8.23 (dd, J 8.5,
1.7 Hz, 1H), 8.06 (dd, J 7.6, 0.88 Hz, 1H), 7.65 (dd, J 8.2, 1.1 Hz, 1H),
7.48 ± 7.43 (m, 2H), 7.16 (dd, J 8.5, 5.3 Hz, 2H), 6.82 (t, J 6.7 Hz, 2H),
3.75 (s, 2H), 3.45 (t, J 6.7 Hz, 2H), 2.83 (t, J 6.7 Hz, 2H); 13C NMR
(100 MHz, [D6]DMSO): d 165.8, 165.1 (d, J 260 Hz), 160.8, 150.1, 147.9,
138.2, 136.4, 132.9, 131.5, 128.9, 128.8, 128.7, 124.4, 120.9, 113.7 (d, J
260 Hz), 41.0, 38.6, 29.9.
28.8; HRMS (MALDI-FTMS): calcd for C18H18F2N2O2S2 [MH] :
397.0778, found: 397.0846.
Compound 88: Rf 0.72 (silica gel, EtOAc/hexanes 1:1); IR (film): nÄmax
1
3388, 1662, 1513, 1430, 1287, 1226, 1018, 950 cm
;
1H NMR (400 MHz,
Compound 65: Rf 0.77 (silica gel, EtOAc/hexanes 1:1); 1H NMR
(400 MHz, CD3OD): d 7.31 (s, 1H), 7.12 (q, J 7.3 Hz, 1H), 6.96 (d,
J 7.0 Hz, 1H), 6.88 (d, J 9.7 Hz, 1H), 6.78 ± 6.76 (m, 1H), 6.21 ± 6.16 (m,
2H), 3.80 (s, 4H), 3.34 (t, J 6.4 Hz, 2H), 2.44 (t, J 6.7 Hz, 2H); 13C NMR
(100 MHz, [D6]DMSO): d 163.2, 162.1 (d, J 241 Hz), 151.3, 150.1, 142.9,
139.6 (d, J 7.6 Hz), 130.2 (d, J 7.6 Hz), 124.9, 115.4 (d, J 20.9 Hz),
113.0 (d, J 20.9 Hz), 110.9, 109.1, 37.9, 36.8, 34.6, 28.8; HRMS (MALDI-
CD3OD): d 7.27 ± 7.28 (m, 6H), 7.10 (d, J 6.4 Hz, 1H), 6.84 (dd, J 6.7,
1.2 Hz, 2H), 6.80 (dd, J 5.6, 1.2 Hz, 1H), 3.96 (s, 2H), 3.86 (s, 2H), 3.49 (t,
J 5.3 Hz, 2H), 2.58 (t, J 5.4 Hz, 2H); 13C NMR (125 MHz, [D6]DMSO):
d 163.2, 158.1, 158.2, 151.8, 151.3, 151.2, 133.1, 133.0, 129.8, 128.5, 128.4,
116.3, 36.9, 36.5, 27.8; HRMS (MALDI-FTMS): calcd for C18H19ClN2O3S2
[MNa] : 433.0423, found: 433.0414.
Compound 73: This compound was prepared by a route similar to that used
for the synthesis of psammaplin A[1] with the following two modifications:
Bromotyrosine was replaced by chlorotyrosine and cystamine was replaced
by 1,6-diaminohexane. 73: Rf 0.11 (silica gel, EtOAc/hexanes 1:1); IR
FTMS): calcd for C16H17FN2O3S2 [MNa] : 391.0562, found: 391.0573.
Compound 66: Rf 0.68 (silica gel, EtOAc/hexanes 1:1); IR (film): nÄmax
3403, 1663, 1523, 1442, 1211, 1023 cm 1; 1H NMR (400 MHz, CD3OD): d
7.43 ± 7.41 (m, 1H), 7.19 ± 7.18 (m, 1H), 7.14 ± 7.10 (m, 1H), 6.97 (d, J
7.6 Hz, 1H), 6.88 ± 6.86 (m, 2H), 6.79 ± 6.74 (m, 1H), 3.80 (s, 2H), 3.49 (t,
J 6.7 Hz, 2H), 2.80 (t, J 6.7 Hz, 2H); 13C NMR (100 MHz, [D6]DMSO):
d 163.2, 163.0, 162.0 (d, J 260 Hz), 151.2, 139.6 (d, J 7.6 Hz), 135.0 (d,
J 8.5 Hz), 132.4, 130.1 (d, J 8.6 Hz), 128.2, 124.8, 115.4 (d, J 20.9 Hz),
112.9 (d, J 20.9 Hz), 37.8, 36.7, 28.7.
1
(film): nÄmax 3403, 1658, 1511, 1430, 1289, 1219, 1022, 710 cm 1; H NMR
(400 MHz, CD3OD): d 7.27 (brs, 1H), 7.10 (d, J 6.4 Hz, 1H), 6.84 (d,
J 6.7 Hz, 1H), 3.87 (s, 2H), 3.28 (q, J 5.6 Hz, 2H), 1.55 (m, 2H), 1.36 ±
1.31 (m, 2H); 13C NMR (125 MHz, [D6]DMSO): d 164.8, 152.4, 151.6,
130.4, 129.3, 128.7, 120.3, 116.4, 39.1, 27.8, 13.4; MS (ESI): calcd for
C22H24Cl2N4O6S2 [M H] : 573, found: 573.
Compounds 82, 84, and 87 were prepared in the same manner as described
for compound 73 with the exception that 1,6-diaminohexane was replaced
by amine 78, 76, or 85, respectively.
Compound 67: Rf 0.56 (silica gel, EtOAc/hexanes 1:1); IR (film): nÄmax
3404, 1663, 1514, 1426, 1290, 1222, 1021, 777 cm 1;1H NMR (400 MHz,
CD3OD): d 7.88 ± 7.87 (m, 1H), 7.38 ± 7.36 (m, 2H), 7.24 ± 7.21 (m, 1H),
7.10 (brs, 1H), 6.93 ± 6.92 (m, 1H), 6.69 ± 6.67 (m, 1H), 3.68 (s, 2H), 3.55 ±
3.54 (m, 2H), 2.86 ± 2.85 (m, 2H); 13C NMR (100 MHz, [D6]DMSO): d
163.2, 150.8, 150.4, 138.9, 133.4, 131.3, 128.9, 128.4, 127.5, 127.4, 118.2, 115.4,
37.2, 36.3, 26.8; HRMS (MALDI-FTMS): calcd for C17H15Cl3N2O3S2
Compound 82: Rf 0.69 (silica gel, EtOAc/hexanes 1:1); IR (film): nÄmax
1
3383, 3048, 2919, 1658, 1511, 1427, 1290, 1213, 1016, 702 cm
;
1H NMR
(400 MHz, CD3OD): d 8.81 ± 8.71 (m, 6H), 8.55 (dd, J 8.5, 2.1 Hz, 1H),
8.28 (d, J 8.5 Hz, 1H), 5.31 (s, 2H), 5.23 (s, 2H), 4.92 (t, J 6.7 Hz, 2H),
4.04 (t, J 6.7 Hz, 2H); 13C NMR (125 MHz, CD3OD): d 165.9, 153.3,
152.9, 139.9, 131.6, 130.4, 130.2, 129.8, 129.6, 128.1, 121.4, 117.5, 39.8, 36.7,
31.5, 28.9.
[MNa] : 486.9487, found: 486.9491.
Compound 68: Rf 0.02 (silica gel, EtOAc/hexanes 1:1); IR (film): nÄmax
1
3412, 1654, 1513, 1428, 1288, 1215, 1017, 685 cm
;
1H NMR (400 MHz,
CD3OD): d 7.10 ± 7.09 (m, 1H), 7.03 ± 7.00 (m, 3H), 6.94 ± 6.91 (m, 1H),
6.69 ± 6.66 (m, 1H), 3.68 (s, 2H), 3.46 ± 3.43 (m, 2H), 2.73 ± 2.70 (m, 2H),
2.44 (s, 6H); 13C NMR (100 MHz, [D6]DMSO): d 163.2, 160.8, 151.5,
141.3, 138.4, 131.6, 130.6, 129.9, 128.5, 128.3, 119.5, 116.4, 38.5, 27.8, 21.7,
Compound 84: Rf 0.65 (silica gel, EtOAc/hexanes 1:1); IR (film): nÄmax
1
3196, 1658, 1507, 1431, 1290, 1213, 1017, 691 cm
;
1H NMR (400 MHz,
CD3OD): d 8.83 ± 8.71 (m, 5H), 8.67 (t, J 7.0 Hz, 1H), 8.54 (dd, J 8.2,
2.0 Hz, 1H), 8.28 (d, J 8.2 Hz, 1H), 5.31 (s, 2H), 4.87 ± 4.82 (m, 4H), 4.41
(t, J 7.3 Hz, 2H), 3.32 ± 3.30 (m, 2H); 13C NMR (125 MHz, CD3OD): d
162.1, 153.5, 152.5, 138.1, 131.5, 130.4, 130.3, 130.1, 129.8, 127.1, 121.5, 117.5,
39.4, 31.8, 30.3, 28.9; HRMS (MALDI-FTMS): calcd for C18H19ClN2O3S2
21.0; HRMS (MALDI-FTMS): calcd for C19H21ClN2O3S2 [MNa] :
447.0574, found: 447.0566.
Compound 69: Rf 0.67 (silica gel, EtOAc/hexanes 1:1); IR (film): nÄmax
3390, 1666, 1527, 1457, 1362, 1314, 1201, 1019, 845, 775, 717 cm 1; 1H NMR
(400 MHz, CD3OD): d 6.95 ± 6.88 (m, 3H), 6.66 (brd, J 6.4 Hz, 2H),
6.53 (tm, J 9.1 Hz, 1H), 3.70 (s, 2H), 3.36 (t, J 6.8 Hz, 2H), 2.63 (t,
[MH] : 379.0878, found: 379.0873.
Compound 87: Rf 0.63 (silica gel, EtOAc/hexanes 1:1); IR (film): nÄmax
1
3393, 2931, 1658, 1510, 1429, 1289, 1219, 1014, 950, 701 cm
;
1H NMR
Chem. Eur. J. 2001, 7, No. 19
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
0947-6539/01/0719-4309 $ 17.50+.50/0
4309