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J. Moeker et al. / Bioorg. Med. Chem. 20 (2012) 2392–2404
(d, J = 9.3 Hz, 1H, CHNH), 8.20 (br s, 1H, NH-CH2), 7.78 (d, J = 8.2 Hz,
2H, Harom–c/d), 7.40 (d, J = 8.1 Hz, 2H, Harom-a/b), 7.30 (s, 2H,
SO2NH2), 5.83 (br s, 1H, H-1), 5.34–5.28 (m, 2H, H-3, H-4), 5.05
(vt, J = 8.9 Hz, 1H, H-2), 4.83 (dd, J = 4.3, 15.9 Hz, 1H, NHCH2a),
4.74 (dd, J = 5.6, 15.8 Hz, 1H, NHCH2b), 4.30–4.24 (m, 1H, H-5),
4.07–4.01 (m, 2H, H-6a/b), 2.12, 1.99, 1.99, 1.94 (4 ꢂ s, 12H,
OCOCH3), assignments were confirmed by 1H–1H gCOSY. 13C
NMR (125 MHz, CDCl3) d = 184.0 (C@S), 170.3, 169.8, 169.5, 169.3
(COCH3), 142.9 (Carom-SO2NH2), 142.7 (Carom), 127.3 (CHarom-a/b),
125.6 (CHarom-c/d), 81.9 (C-1), 71.2 (C-5), 70.7 (C-3), 68.5 (C-2),
67.5 (C-4), 61.2 (C-6), 46.6 (NHCH2), 20.5, 20.4, 20.4, 20.3
(OCOCH3), assignments were confirmed by 1H–13C HSQC. HRMS:
Calcd for C22H29N3O11S2Na+ 598.1136, Found 598.1132.
75.5 (C-3), 74.9 (C-4), 73.7 (C-5), 71.4 (C-2), 70.1 (C-20), 69.7 (C-
30), 68.35 (C-40), 68.33 (C-50), 63.2 (C-6), 61.7 (C-60), 20.6, 20.6,
20.4, 20.4, 20.4, 20.3, 20.2 (OCOCH3), assignments were confirmed
by 1H–13C HSQC.
4.1.12. N-[4-(Aminosulfonyl)benzyl]-N0-(20,200,30,300,40,60,600-
hepta-O-acetyl-D-maltosyl)thiourea (18)
The title compound 18 was prepared from amine 2 and isothi-
ocyanate 7 according to general procedure 1 to give a white solid.
mp = 124–126 °C; 1H NMR (500 MHz, DMSO-d6) d = 8.27 (br s, 1H,
NH-CH2), 8.11 (br s, 1H, CHNH), 7.77 (d, J = 7.8 Hz, 2H, Harom–c/d),
7.40 (d, J = 8.0 Hz, 2H, Harom-a/b), 7.29 (s, 2H, SO2NH2), 5.78 (br s,
1H, H-1), 5.39–5.28 (m, 2H, H-10, H-3), 5.23 (vt, J = 10.0 Hz, 1H,
H-30), 4.99 (vt, J = 9.7 Hz, 1H, H-40), 4.91–4.71 (m, 4H, H-2, H-20,
NH-CH2), 4.34 (dd, J = 1, 11.9 Hz, 1H, H-6a), 4.21–4.11 (m, 2H, H-
5, H-6b), 4.06–3.89 (m, 4H, H-4, H-50, H-60a/b), 1.88, 1.86, 1.84,
1.82, 1.80, 1.78 (6 ꢂ s, 21H, OCOCH3), assignments were confirmed
by 1H–1H gCOSY. 13C NMR (125 MHz, CDCl3) d = 178.0 (C@S), 170.1,
4.1.9. N-[4-(Aminosulfonyl)phenethyl]-N0-(20,30,40,60-tetra-O-
acetyl-D-galactopyranosyl)thiourea (15)
The title compound 15 was prepared from amine 3 and isothi-
ocyanate 6 according to general procedure 1 to give a white solid.
mp = 113–115 °C; 1H NMR (500 MHz, DMSO-d6) d = 8.04 (d,
J = 9.0 Hz, 1H, NHCH), 7.75 (d, J = 8.0 Hz, 2H, Harom–c/d), 7.71 (br
s, 1H, NH-CH2), 7.40 (d, J = 8.1 Hz, 2H, Harom-a/b), 7.28 (s, 2H,
SO2NH2), 5.80 (br s, 1H, H-1), 5.32–5.26 (m, 2H, H-3, H-4), 5.01
(vt, J = 7.6 Hz, 1H, H-2), 4.28–4.20 (m, 1H, H-5), 4.02–3.98 (m,
170.0, 169.9, 169.6, 169.5, 169.2 (7 ꢂ COCH3), 142.7 (Carom
-
SO2NH2), 130.2 (Carom), 127.4 (CHarom-a/b), 125.6 (CHarom-c/d),
95.3 (C-10), 74.9 (C-1), 73.7 (C-3), 72.8 (C-50), 71.2 (C-2), 69.5 (C-
20), 68.94 (C-30), 68.92 (C-5), 68.0 (C-40), 67.8 (C-4), 62.9 (C-6),
62.9 (C-60), 46.7 (NH-CH2), 20.6, 20.6, 20.4, 20.4, 20.3, 20.3
(7 ꢂ OCOCH3), assignments were confirmed by 1H–13C HSQC.
HRMS: Calcd for C34H45N3O19S2Na+ 886.1981, Found 886.2003.
2H, H-6a/b), 3.68 (br s, 2H, CH2NH), 2.90 (br s, 2H, CH2Carom
)
2.10, 1.98, 1.92 (3 ꢂ s, 12H, OCOCH3), assignments were confirmed
by 1H–1H gCOSY. 13C NMR (125 MHz, DMSO-d6) d = 183.6 (C@S),
169.8, 169.5, 169.3 (4 ꢂ C@O), 143.3 (Carom-SO2NH2), 142.1 (Carom),
129.1 (CHarom-a/b), 125.7 (CHarom-c/d), 81.6, (C-1), 71.1 (C-5), 70.7
(C-3), 68.4 (C-2), 67.5 (C-4), 61.2 (C-6), 44.8 (NH-CH2), 34.0
4.1.13. N-[4-(Aminosulfonyl)phenylethyl]-N0-(20,200,30,300,400,60,600-
hepta-O-acetyl-D-maltosyl)thiourea (19)
The title compound 19 was prepared from amine 3 and isothi-
ocyanate 7 according to general procedure 1 to give a white solid.
mp = 130–131 °C; 1H NMR (500 MHz, DMSO-d6) d = 7.94 (br s, 1H,
NH-CH2), 7.80 (br s, 1H, CHNH), 7.75 (d, J = 8.8 Hz, 2H, Harom–c/d),
7.40 (d, J = 8.2 Hz, 2H, Harom-a/b), 7.28 (s, 2H, SO2NH2), 5.76 (br s,
1H, H-1), 5.37–5.29 (m, 2H, H-10, H-3), 5.23 (vt, J = 10.1 Hz, 1H,
H-30), 4.99 (vt, J = 9.6 Hz, 1H, H-40), 4.87 (dd, J = 10.5, 3.5 Hz, 1H,
H-20), 4.78 (vt, J = 8.9 Hz, 1H, H-2), 4.33 (dd, J = 1.0, 12.1 Hz, 1H,
H-6a), 4.20–4.13 (m, 2H, H-60a, H-6b), 4.04–3.95 (m, 2H, H-50, H-
60b), 3.94–3.90 (m, 2H, H-4, H-5), 3.73–3.63 (m, 2H, NH-CH2),
2.97–2.85 (CH2Carom), 2.06, 2.03, 2.01, 1.99, 1.96, 1.93 (6 ꢂ s, 21H,
OCOCH3), assignments were confirmed by 1H–1H gCOSY. 13C
NMR (125 MHz, DMSO-d6) d = 177.3 (C@S), 170.0, 169.9, 169.8,
169.5, 169.42, 169.40, 169.1 (COCH3), 143.3 (Carom-SO2NH2),
142.1 (Carom), 129.1 (CHarom-a/b), 125.7 (CHarom-c/d), 95.3 (C-10),
82.0 (C-1), 74.9 (C-3), 73.6 (C-4), 72.7 (C-5), 71.0 (C-2), 69.4 (C-
20), 68.9 (C-30), 67.9 (C-50), 67.8 (C-40), 62.9 (C-6), 61.4 (C-60), 44.8
(CH2NH), 30.6 (CH2Carom), 20.6, 20.5, 20.4, 20.4, 20.3, 20.3, 20.2
(OCOCH3), assignments were confirmed by 1H–13C HSQC. HRMS:
(CH2Carom), 20.5, 20.4, 20.4, 20.3 (OCOCH3), assignments were con-
C HSQC. HRMS: Calcd for C23H32N3O11S2
590.1473, Found 590.1493.
firmed by 1H–13
+
4.1.10. N-[4-(Aminosulfonyl)phenylhydrazido]-N0-(20,30,40,60-
tetra-O-acetyl-D-galactopyranosyl)thiourea (16)
The title compound 16 was prepared from amine 4 and isothi-
ocyanate 6 according to general procedure 1 to give a white solid.
mp = 194–195 °C; 1H NMR (500 MHz, DMSO-d6) d = 10.43 (s, 1H,
NH), 9.86 (s, 1H, NH), 8.61 (d, J = 8.5 Hz, 1H, CHNH), 8.06 (d,
J = 8.0 Hz, 2H, Harom–c/d), 7.93 (d, J = 8.0 Hz, 2H, Harom-a/b), 7.53
(s, 2H, SO2NH2), 5.84 (vt, J = 9.1 Hz, 1H, H-1), 5.34–5.26 (m, 2H,
H-3, H-4), 5.17 (vt, J = 9.3 Hz, 1H, H-2), 4.32–4.22 (m, 1H, H-5),
4.07–3.99 (m, 2H, H-6a/b), 2.08, 2.00, 1.94, 1.89 (4 ꢂ s, 12H,
OCOCH3), assignments were confirmed by 1H–1H gCOSY. 13C
NMR (125 MHz, DMSO-d6) d = 183.4 (C@S), 169.8, 169.4, 169.3
(4 ꢂ C@O), 166.6 (NHC@O), 146.7 (Carom-SO2NH2), 128.6 (CHarom
-
a/b), 125.3 (CHarom-c/d), 82.4 (C-1), 71.6 (C-5), 70.8 (C-4), 68.0
(C-2), 67.6 (C-3), 61.2 (C-6), 20.5, 20.4, 20.3 (4 ꢂ OCOCH3), HRMS:
+
Calcd for C35H48N3O19S2 878.2318, Found 878.2296.
+
Calcd for C22H29N4O12S2 605.1218, Found 605.1231.
4.1.14. N-[4-(Aminosulfonyl)phenylhydrazido]-N0-
4.1.11. N-[4-(Aminosulfonyl)phenyl]-N0-(20,200,30,300,400,60,600-
(20,200,30,300,400,60,600-hepta-O-acetyl-
D-maltosyl)thiourea (20)
hepta-O-acetyl-
D
-maltosyl)thiourea (17)
The title compound 20 was prepared from amine 4 and isothi-
ocyanate 7 according to general procedure 1 to give a white solid.
mp = 138–139 °C; 1H NMR (500 MHz, DMSO-d6) d = 10.49 (s, 1H,
NH), 9.87 (s, 1H, NH), 8.44 (s, 1H, NHCH), 8.02 (d, J = 8.3 Hz, 2H, Har-
om–c/d), 7.91 (br s, 2H, Harom-a/b), 7.49 (s, 2H, SO2NH2), 5.84 (vt,
J = 8.4 Hz, 1H, H-1), 5.34–5.26 (m, 2H, H-10, H-30), 5.21 (t,
J = 9.9 Hz, 1H, H-3), 5.00–4.94 (m, 2H, H-2, H-4), 4.85 (dd,
J = 10.5, 3.3 Hz, 1H, H-20), 4.34 (d, J = 12.8 Hz, 1H, H-6a), 4.22–
4.10 (m, 2H, H-50, H-6b), 4.02–3.94 (m, 3H, H-5, H-60a/b), 3.85
(br s, 1H, H-40), 2.05, 2.01, 1.99, 1.98, 1.95, 1.92, 189 (7 ꢂ s, 21 H,
OCOCH3), assignments were confirmed by 1H–1H gCOSY. 13C
NMR (125 MHz, DMSO-d6) d = 179.7 (C@S), 170.0, 169.9, 169.9,
The title compound 17 was prepared from amine 1 and isothi-
ocyanate 7 according to general procedure 1 to give a yellow solid.
mp = 178–179 °C; 1H NMR (500 MHz, DMSO-d6) d = 10.09 (s, 1H,
NH), 8.30 (br s, 1H, CHNH), 7.75 (d, J = 8.8 Hz, 2H, Harom–c/d),
7.69 (d, J = 8.2 Hz, 2H, Harom-a/b), 7.28 (s, 2H, SO2NH2), 5.85 (br s,
1H, H-1), 5.40 (vt, J = 8.6 Hz, 1H, H-3), 5.32 (d, J = 3.3, 1H, H-10),
5.24 (vt, J = 10.0 Hz, 1H, H-30), 4.99 (vt, J = 9.9 Hz, 1H, H-4), 4.94–
4.84 (m, 2H, H-2, H-20), 4.35 (dd, J = 1.0, 11.5 Hz, 1H, H-6a), 4.21–
4.13 (m, 2H, H-60a, H-6b), 4.05–3.92 (m, 4H, H-40, H-50, H-5, H-
60b), 2.06, 2.02, 2.01, 1.99, 1.98, 1.97, 1.96 (7 ꢂ s, 21H, OCOCH3),
assignments were confirmed by 1H–1H gCOSY. 13C NMR
(125 MHz, DMSO-d6) d = 181.9 (C@S), 170.1, 169.9, 169.8, 169.6,
169.5, 169.5, 169.4 (COCH3), 142.0 (Carom-SO2NH2), 141.1 (Carom),
126.2 (CHarom-a/b), 122.0 (CHarom-c/d), 95.3 (C-10), 82.0 (C-1),
169.5, 169.4, 169.4, 169.1 (COCH3), 166.3 (NHC@O), 146.8 (Carom
-
SO2NH2), 140.6 (Carom), 128.5 (CHarom-a/b), 125.3 (CHarom-c/d),
95.3 (C-10), 82.9 (C-1), 79.2 (C-3), 74.5 (C-4), 73.6 (C-5), 72.9