3.96 (broad d, 1H, H-4_Gal), 3.57–3.93 (m, 17H, H-5_Gal ϩ
H-6a_Gal ϩ H-6b_Gal ϩ H-4_Neu_A ϩ H-5_Neu_A ϩ
H-6_Neu_A ϩ H-7_Neu_A ϩ H-9b_Neu_A ϩ H-4_Neu_B ϩ
H-5_Neu_B ϩ H-6_Neu_B ϩ H-7_Neu_B ϩ H-8_Neu_B ϩ
H-9a_Neu_B ϩ H-9b_Neu_B ϩ OCHaHb ϩ OCHaHb),
3.52 (dd, 1H, H-2_Gal), 2.99 (t, 2H, J = 7.5, CH2NH2), 2.77
(dd, 1H, J3e,4 = 4.5, J3e,3a = 12.2, H-3e_Neu_A), 2.68 (dd, 1H,
J3e,4 = 4.5, J3e,3a = 12.2, H-3e_Neu_B), 2.07, 2.03 (2 × s, 2 ×
3H, 2 × NHAc), 1.74 (‘t’, 1H, H-3a_Neu_B), 1.73 (‘t’, 1H,
H-3a_Neu_A), 1.59–1.63 (m, 4H, chain), 1.28–1.41 (m, 14 H,
chain). Found: M (High Res. ESMS) 932.44534. Calc. for
C39H70N3O22: MHϩ 932.44510.
MeOH (10 ml), was added a solution of NaOMe in MeOH
(1.5 M, 0.2 ml), and the mixture was stirred overnight at room
temperature. The solvent was removed under reduced pressure,
and the residue was dissolved in MeOH (5 ml); H2O (5 drops)
was added, and the mixture was stirred for another 24 h. The
solution was neutralized with a piece of dry-ice and then con-
centrated. The residue was dissolved in MeOH (5 ml), 10%
Pd(OH)2-C (50 mg) was added and the mixture was stirred
under an atmosphere of H2 for 17 h. The catalyst was filtered
off, and washed with more MeOH (3 × 5 ml), and the combined
filtrate was concentrated. Compound 4 (9.2 mg, 89%) was
obtained by HPLC chromatography on a C18 column using
1
H2O as eluent. [α]D ϩ1Њ (c 0.7, H2O). H NMR (D2O): δ 4.53
Methyl O-[methyl 5-acetamido-8-O-(5-acetamido-4,7,8,9-
tetra-O-acetyl-3,5-dideoxy-D-glycero-ꢀ-D-galacto-non-2-ulopyr-
anosylano-1Ј,9-lactone)-4,7-di-O-acetyl-3,5-dideoxy-D-glycero-
ꢀ-D-galacto-non-2-ulopyranosylonate]-(2 3)-2,6-di-O-benzyl-
ꢁ-D-galactopyranosyl-(1 4)-2,3,6-tri-O-benzyl-ꢁ-D-gluco-
pyanoside (30). A mixture containing the acceptor 19 (41 mg,
51 µmol), donor 8 (94 mg, 100 µmol) and 4 Å molecular sieves
(300 mg) in anhydrous CH3CN (1.5 ml) was stirred under Ar
overnight and the mixture was cooled to Ϫ30 ЊC. NIS (24 mg,
100 µmol) was added and TfOH (10 µl) was added dropwise 10
min later. After stirring for 3 days at the same temperature,
Et3N (0.5 ml) was added to quench the reaction. The mixture
was diluted with CH2Cl2 (10 ml) and the insoluble material
was filtered off and washed with more CH2Cl2 (3 × 10 ml); the
combined organic solution was washed with 10% Na2S2O3
solution, dried and evaporated. The residue was first purified by
chromatography on silica gel (30 50% acetone–toluene) to
afford compound 30 (31.2 mg), which was impure according to
NMR. Pure 30 (20.9 mg, 25%) was obtained by HPLC chroma-
tography on silica gel (0 2% MeOH–CH2Cl2). [α]D Ϫ9.5Њ
(d, 1H, J1,2 = 7.9, H-1_Gal), 4.42 (d, 1H, J1,2 = 7.9, H-1_Glc),
4.19 (dd, 1H, J8,9a = 3.9, J9a,9b = 12.3, H-9a_Neu_A), 4.15 (m,
1H, H-8a_Neu_A), 4.10 (dd, 1H, J2,3 = 3.1, J3,4 = 9.9, H-3_Gal),
4.03 (dd, 1H, J5,6a = 2.2, J6a,6b = 12.3, H-6a_Glc), 3.98 (br d,
1H, H-4_Gal), 3.59–3.93 (m, 19 H, H-3_Glc ϩ H-4_Glc ϩ
H-5_Glc ϩH-6b_Glc ϩ H-5_Gal ϩ H-6a_Gal ϩH-6b_Gal ϩ
H-4_Neu_A ϩ H-5_Neu_A ϩ H-6_Neu_A ϩ H-7_Neu_A ϩ
H-9b_Neu_A ϩ H-4_Neu_B ϩ H-5_Neu_B ϩ H-6_Neu_B
ϩH-7_Neu_B ϩH-8_Neu_B ϩ H-9a_Neu_B ϩ H-9b_Neu_B),
3.59 (s, 3H, OMe), 3.58 (dd, 1H, H-2_Gal), 3.32 (‘t’, 1H, J2,3
≈
8.9, H-2_Glc), 2.79 (dd, 1H, J3e,4 = 4.6, J3e,3a = 12.3, H-
3e_Neu_A), 2.69 (dd, 1H, J3e,4 = 4.6, J3e,3a = 12.5, H-3e_Neu_B),
2.08, 2.04 (2 × s, 2 × 3H, 2 × Ac), 1.76 (‘t’, 1H, H-3a_Neu_A),
1.75 (‘t’, 1H, H-3b_Neu_B). Found: MϪ (High Res. ESMS)
468.15414. Calc. for C35H54N2O27: M2Ϫ 468.15353.
11-Azidoundecyl O-[methyl 5-acetamido-8-O-(5-acetamido-
4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-ꢀ-D-galacto-non-2-
ulopyranosylano-1Ј,9-lactone)-4,7-di-O-acetyl-3,5-dideoxy-D-
glycero-ꢀ-D-galacto-non-2-ulopyranosylonate]-(2 3)-O-(2,6-di-
O-benzyl-ꢁ-D-galactopyranosyl)-(1 4)-2,3,6-tri-O-benzyl-ꢁ-D-
glucopyanoside (31). Compound 31 was obtained according to
a procedure similar to 30 by reacting acceptor 25 (45 mg,
50 µmol) with donor 8 (94 mg, 100 µmol). Pure 31 (24.0 mg,
29%) was obtained by HPLC chromatography on silica gel
1
(c 0.6, CHCl3). H NMR (CDCl3): δ 7.19–7.40 (m, 25H, Bn),
5.68 (d, 1H, J5,NH = 9.9, NH_Neu_B), 5.34 (ddd, 1H, J3e,4 = 5.3,
J3a,4 ≈ J4,5 = 11.2, H-4_Neu_A), 5.33 (dd, 1H, J6,7 = 2.4, J7,8
=
9.2, H-7_Neu_A), 5.28 (d, 1H, J5,NH = 10.4, NH_Neu_A), 5.14
(ddd, 1H, J8,9a = 2.8, J8,9b = 5.0, H-8_Neu_A), 5.08 (ddd, 1H,
1
J3e,4 = 5.1, J3a,4 ≈ J4,5 = 11.0, H-4_Neu_B), 5.04 (dd, 1H, J6,7
=
(0 2% MeOH–CH2Cl2). [α]D Ϫ12Њ (c 1.0, CHCl3). H NMR
1.8, J7,8 = 8.2, H-7_Neu_B), 4.96 (d, 1H, J = 10.4, Bn), 4.84 (d,
1H, J = 11.2, Bn), 4.72 (d, 1H, J = 10.6, Bn), 4.70 (d, 1H, J =
11.5, Bn), 4.69 (d, 1H, J = 11.0, Bn), 4.62 (d, 1H, J = 12.2, Bn),
4.60 (d, 1H, J = 12.6, Bn), 4.46 (d, 1H, J1,2 = 7.6, H-1_Gal), 4.46
(d, 1H, J = 12.1, Bn), 4.41 (d, 1H, J = 11.8, Bn), 4.31–4.36 (m,
2H, H-9a_Neu_B ϩ Bn), 4.26 (d, 1H, J1,2 = 7.9, H-1_Glc), 4.25
(dd, 1H, J8,9a = 2.7, J9a,9b = 12.8, H-9a_Neu_A), 4.16–4.29 (m,
2H, H-8_Neu_B ϩ H-5_Neu_A), 4.10 (dd, 1H, J8,9b = 3.3,
H-9b_Neu_B), 4.06 (ddd, 1H, H-5_Neu_B), 4.02 (dd, 1H,
(CDCl3): δ 7.19–7.41 (m, 25H, Bn), 5.64 (d, 1H, J5,NH = 10.1,
NH_Neu_B), 5.34 (ddd, 1H, J3e,4 = 5.4, J3a,4 ≈ J4,5 = 10.9,
H-4_Neu_A), 5.33 (dd, 1H, J6,7 = 1.8, J7,8 = 9.0, H-7_Neu_A),
5.24 (d, 1H, J5,NH = 10.2, NH_Neu_A), 5.14 (ddd, 1H, J8,9a
2.9, J8,9b = 4.9, H-8_Neu_A), 5.08 (ddd, 1H, J3e,4 = 5.1, J3a,4
=
≈
J4,5 = 10.9, H-4_Neu_B), 5.04 (dd, 1H, J6,7 = 1.8, J7,8 = 8.1,
H-7_Neu_B), 4.95 (d, 1H, J = 10.5, Bn), 4.88 (d, 1H, J = 10.5,
Bn), 4.73 (d, 1H, J = 11.0, Bn), 4.71 (d, 1H, J = 11.8, Bn),
4.70 (d, 1H, J = 11.0, Bn), 4.60 (d, 1H, J = 12.2, Bn), 4.59 (d,
1H, J = 11.3, Bn), 4.47 (d, 1H, J1,2 = 7.6, H-1_Gal), 4.46 (d, 1H,
J = 12.2, Bn), 4.41 (d, 1H, J = 11.8, Bn), 4.34 (d, 1H, J1,2 = 7.8,
H-1_Glc), 4.29–4.34 (m, 2H, H-9a_Neu_B ϩ Bn), 4.25 (dd, 1H,
J9a,9b = 12.7, H-9a_Neu_A), 4.16–4.20 (m, 2H, H-8_Neu_B ϩ
H-5_Neu_A), 4.10 (dd, J9a,9b = 12.1, H-9b_Neu_B), 4.06 (ddd,
1H, H-5_Neu_B), 4.02 (dd, 1H, H-9b_Neu_A), 3.98 (‘t’, 1H,
H-4_Glc), 3.96 (dd, 1H, J5,6 = 10.7, H-6_Neu_A), 3.88–3.94 (m,
J8,9b = 4.9, J9a,9b = 12.6, H-9b_Neu_A), 4.00 (‘t’, 1H, J3,4 ≈ J4,5
=
9.5, H-4_Glc), 3.96 (dd, 1H, J5,6 = 10.4, H-6_Neu_A), 3.93 (dd,
1H, J5,6 = 10.6, H-6_Neu_B), 3.89 (br ‘d’, 1H, H-4_Gal), 3.83
(dd, 1H, J2,3 = 9.3, J3,4 = 3.3, H-3_Gal), 3.80 (s, 3H, CO-
OMe_Neu_B), 3.78 (dd, 1H, J5,6a = 4.4, H-6a_Glc), 3.73 (dd,
1H, J5,6b = 1.8, J6a,6b = 11.0, H-6b_Glc), 3.68 (dd, 1H, J5,6a
=
7.3, J6a,6b = 9.7, H-6a_Gal), 3.54 (s, 3H, OMe), 3.53 (‘t’, 1H,
J2,3 ≈ J3,4 = 9.3, H-3_Glc), 3.49 (dd, 1H, J2,3 = 9.3, H-2_Gal),
3.47 (dd, 1H, J5,6b = 5.3, H-6b_Gal), 3.33–3.38 (m, 3H, H-5_Glc
ϩ H-5_Gal ϩ H-2_Glc), 2.40 (dd, 1H, J3a,3e = 13.2,
H-3e_Neu_B), 2.39 (dd, 1H, J3a,3e = 13.5, H-3e_Neu_A), 2.10
(‘t’, 1H, H-3a_Neu_A), 2.09, 2.09, 2.01, 1.99, 1.98, 1.94, (6 × s,
6 × 3H, 6 × OAc),m 1.90 (‘t’ 1H, H-3a_Neu_B), 1.89, 1.87 (2 ×
s, 2 × 3H, 2 × OAc). Found: C, 54.3, H, 8.9, N, 10.9; M (High
Res. ESMS) 398.22632. Calc. for C17H33N3O6 (C17H33N3O6Na):
C, 54.4, H, 8.9, N, 11.2%; MNaϩ 398.22670.
3H, H-6_Neu_B ϩ H-4_Gal ϩ OCHaHb), 3.83 (dd, 1H, J2,3
9.3, J3,4 = 3.5, H-3_Gal), 3.80 (s, 3H, COOMe_Neu_B), 3.77
(dd, 1H, J5,6a = 4.7, J6a,6b = 11.5, H-6a_Glc), 3.73 (dd, 1H, J5,6b
=
=
2.3, H-6b_Glc), 3.68 (dd, 1H, J5,6a = 7.2, J6a,6b = 9.6, H-6a_Gal),
3.52 (‘t’, 1H, J2,3 J3,4 = 9.0, H-3_Glc), 3.44–3.51 (m, 3H, H-
6b_Gal
H-5_Glc ϩ H-5_Gal ϩ H-2_Glc), 3.22 (t, 2H, J 7.0, CH2N3),
2.40 (dd, 1H, J3a,3e = 13.5, H-3e_Neu_B), 2.39 (dd, 1H, J3a,3e
ϩ H-2_Gal ϩ OCHaHb), 3.33–3.40 (m, 3H,
=
13.5, H-3e_Neu_A), 2.09 (‘t’ 1H, H-3a_Neu_B), 2.09, 2.06,
2.01, 1.99, 1.98, 1.94 (6 × s, 6 × 3H, 6 × OAc), 1.91 (‘t’, 1H,
H-3a_Neu_A), 1.89, 1.87 (2 × s, 2 × 3H, 2 × OAc), 1.54–1.66
(m, 4H, CH2_chain), 1.22–1.41 (m, 14H, chain). Found: C,
54.3, H, 8.9, N, 10.9; M (High Res. ESMS) 398.22632. Calc. for
C17H33N3O6 (C17H33N3O6Na): C, 54.4, H, 8.8, N, 11.2%; MNaϩ
398.22670.
Methyl O-[5-acetamido-3,5-dideoxy-D-glycero-ꢀ-D-galacto-
non-2-ulopyranosylonic acid]-(2 8)-O-(5-acetamido-3,5-dide-
oxy-D-glycero-ꢀ-D-galacto-non-2-ulopyranosylonic acid)-(2 3)-
O-(ꢁ-D-galactopyranosyl)-(1 4)-ꢁ-D-glucopyanoside (4). To a
solution of compound 30 (18 mg, 11 µmol) in anhydrous
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2, 1 1 9 9 – 1 2 1 2
1209