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PSEUDOSUGAR ANALOGUES OF CHITOTRIOSE
483
4 H, H-2’, H-3’), 3.12, 3.16 (2 s, 6 H, NMe2), 3.45–4.40 (4 m, 11 H, H-5, H-5@, H-6ab,
H-6@ab, H-3, H-3@, H-4@, H-2, H-2@), 4.42–4.79 (m, 10 H, 5 CH2Ph), 4.91–5.12 (3 dd,
3 H, H-4, H-1, H-1@), 6.45–8.88 (m, 28 H, Ph, H-9, H-10, H-12). MALDI-MS: m/z
1159.3 [M +K] + , 1143.4 [M +Na] + , 1121.3 [M +H] + .
N-{2-Acetamido-4-O-[3-N-(2-acetamido-3,4,6-tri-O-benzyl-2-deoxy-b-D-gluco-
pyranosyl)carboxamidopropanoyl]-3,6-di-O-benzyl-2-deoxy-b-D-glucopyranosyl}-
(3-benzyloxycarbonylamino)propanoic Acid Amide (11). A solution of N-benzyl-
oxycarbonyl-b-alanine (44 mg, 0.2 mmol) and EEDQ (47 mg, 0.19 mmol) in dry
CH2Cl2 (10 mL) was stirred for 6 h and subsequently added to freshly prepared 5 (85
mg, 0.09 mmol). The suspension was vigorously stirred overnight. After concentration,
the remaining colourless solid was suspended in EtOH (20 mL) and stirred for 30 min
at rt. Filtration gave 60 mg (58%) of 11 as a colourless solid, mp 287°C. [a]D22 +9.4 (c
1
0.5, DMSO). H NMR (DMSO-d6): d 1.79 (s, 6 H, 2 NHCOMe), 2.28 (m, 2 H, H-8),
2.41 (m, 4 H, H-2’, H-3’), 3.18 (m, 2 H, H-9), 3.35–3.81 (m, 11 H, H-5, H-5@, H-6ab,
H-6@ab, H-4@, H-3, H-3@, H-2, H-2@), 4.40–4.71 (m, 10 H, 5 CH2Ph), 4.87 (dd, 1 H,
H-4, J 9.2 Hz), 4.99 (m, 4 H, COOCH2Ph, 1-H, 1@-H), 7.18–7.24 (m, 31 H, 6 Ph, NH-
9), 8.01, 8.06 (2 d, 2 H, NH-2, NH-2@, J 9.0 Hz, J 8.5 Hz), 8.42, 8.48 (2 d, 2 H, NH-1,
NH-1@, J 9.1 Hz, J 9.3 Hz). 13C NMR (DMSO-d6): d 22.7, 22.8 (2 NHCOMe), 28.7,
29.8 (C-2’, C-3’), 35.6 (C-8), 36.8 (C-9), 53.7 (C-2, C-2@), 65.2 (COOCH2Ph), 68.4,
68.6 (C-6, C-6@), 70.2 (C-4), 72.3, 72.4, 73.5, 73.9, 74.1 (5 CH2Ph), 74.3 (C-4@), 75.9,
77.8 (C-5, C-5@), 78.4, 78.7 (C-1, C-1@), 80.3, 83.0 (C-3, C-3@), 127.4–138.6 (Ph),
155.9 (CO-3), 169.4, 170.7, 171.1, 171.3 (5 CO). MALDI-MS: m/z 1216.7 [M +K] + ,
1200.8 [M +Na] + , 1178.7 [M +H] + .
Anal. Calcd for C66H75N5O15 ꢃ 1 H2O: C 66.27, H 6.49, N 5.85%; Found: C
66.09, H 6.32, N 5.57%.
N-{2-Acetamido-4-O-[3-N-(2-acetamido-3,4,6-tri-O-benzyl-2-deoxy-b-D-gluco-
pyranosyl)carboxamidopropanoyl]-3,6-di-O-benzyl-2-deoxy-b-D-glucopyranosyl}-
(Na,Nd,No-tris-benzyloxycarbonyl)-L-arginine Amide (12). A solution of N a,N d,No
-tri-benzyloxycarbonyl-L-arginine (119 mg, 0.21 mmol) and EEDQ (47 mg, 0.19 mmol)
in dry CH2Cl2 (5 mL) was stirred for 6 h. This solution was added to 85 mg (0.09 mmol)
of freshly prepared 5. The suspension was vigorously stirred for 18 h, followed by
concentration. The residue was suspended in EtOH (15 mL) and stirred for 30 min.
Filtration gave 12 (100 mg, 75%) as a colourless solid, mp 249–250°C. [a]D22 +10.5
1
(c 0.5, DMSO). H NMR (DMSO-d6): d 1.45–1.60 (m, 6 H, H-9, H-10, H-11), 1.79
(s, 6 H, 2 NHCOMe), 2.35–2.49 (m, 4 H, H-2’, H-3’), 3.35–3.84 (m, 12 H, H-5, H-5@,
H-6ab, H-6@ab, H-4@, H-3, H-3@, H-2, H-2@, H-8), 4.37–4.71 (m, 10 H, 5 CH2Ph),
4.75–5.19 (m, 9 H, H-4, H-1@, H-1, 3 CH2COOPh), 7.16–7.44 (m, 42 H, NH-2, NH-12, 8
Ph), 8.02 (dd, 2 H, NH-2, NH-2@, J 9.6 Hz, J 11.2 Hz), 8.38 (dd, 2 H, NH-1, NH-1@, J 9.2
Hz, J 8.8 Hz), 9.15 (b, 1 H, CNH). 13C NMR (DMSO-d6): d 22.7, 22.8 (2 NHCOMe), 25.1
(C-10), 28.7, 29.8 (C-2’, C-3’, C-9), 44.3 (C-11), 53.3, 53.9, 54.7 (C-2, C-2@, C-8), 65.4,
66.1, 68.1 (3 CH2COOPh), 68.3, 68.6 (C-6, C-6@), 70.2 (C-4), 72.3, 72.4, 73.4, 73.9, 74.1
(5 CH2Ph), 74.4 (C-4@), 75.9, 77.8 (C-5, C-5@), 78.7 (C-1, C-1@), 80.3, 83.0 (C-3, C-3@),
127.5–138.6 (Ph), 154.9, 155.9, 159.7 (3 CH2COOPh), 162.9 (CN), 169.4, 169.5,
171.1, 171.2, 172.5 (5 CO). MALDI-MS: m/z 1569.5 [M +K] + , 1553.5 [M +Na] + ,
1531.5 [M +H] + .