H-3, H-3ꢀ, H-3ꢀꢀ, H-4ꢀ, H-4ꢀꢀ, H-6b), 3.60–3.48 (m, 3H, H-2ꢀꢀ, H-4,
H-6a), 3.40 (s, 3H, OCH3), 3.38–3.20 (m, 3H, H-2ꢀ, H-5bꢀꢀ, H-6bꢀ),
3.19–3.04 (m, 3H, H-5, H-5aꢀꢀ, H-6aꢀ), 2.73 (dd, 1H, J1,2 = 7.8 Hz,
J2,3 = 9.6 Hz, H-2), 1.76 (s, 12H, CH3CO2). 13C NMR (75 MHz,
D2O) (acetate salt) d 181.2 (CH3CO2), 102.7 (C-1), 101.2 (C-1ꢀꢀ),
96.1 (C-1ꢀ), 79.7, 79.0, 71.2, 70.7, 70.6, 70.2, 69.3, 69.1, 66.2, 63.3
(C-2ꢀꢀ), 63.2, 57.5 (OCH3), 55.5 (C-2), 53.7 (C-2ꢀ), 44.3, 40.1 (C-6),
40.0 (C-6ꢀ), 22.7 (CH3CO2).
hydrogenated in pyridine (3.0 mL) in the presence of Pd/C
(20 mg) as described in the general procedures section. The
intermediate was further hydrogenated in AcOH and H2O (10 :
1, v/v, 2.2 mL) in the presence of Pd(OH)2 (20 mg) to give
1
trisaccharide 16 (2.0 mg): H NMR (D2O, 500 MHz) (acetate
salt): d 5.50 (d, 1H, J1 ,2 = 3.5 Hz, H-1ꢀ), 4.60 (d, 1H, J1
=
ꢀ
ꢀ
ꢀꢀ ꢀꢀ
,2
8.5 Hz, H-1ꢀꢀ), 4.34 (d, 1H, J1,2 = 8.0 Hz, H-1), 4.10 (m, 1H,
H-5ꢀ), 4.02–3.95 (m, 3H, H-4, H-4ꢀ, H-5ꢀꢀ), 3.90–3.74 (m, 3H,
H-3, H-3ꢀ, H-6b), 3.72–3.50 (m, 3H, H-3ꢀꢀ, H-5, H-6a), 3.52 (s,
3H, OCH3), 3.45–3.33 (m, 3H, H-2ꢀ, H-2ꢀꢀ, H-6bꢀ), 3.22 (dd, 1H,
Methyl 3-O-(2ꢀ,6ꢀ-diazido-3ꢀ,4ꢀ-di-O-benzyl-2ꢀ,6ꢀ-dideoxy-a-D-
glucopyranosyl)-4-O-(4ꢀꢀ-azido-4ꢀꢀ,6ꢀꢀ-dideoxy-b-D-glucopyranosyl)-
2-azido-2-deoxy-b-D-glucopyranoside (14). A TMSOTf (5 lL)
catalyzed glycosylation of 8 (31 mg, 0.047 mmol) with 6 (24 mg,
0.056 mmol) was performed in CH2Cl2 (2.0 mL) to afford a
trisaccharide (MALDI-TOF: m/z 931.34 [M + Na+]) which was
de-O-acetylated as described. The crude material was purified
by silica gel chromatography (hexane–EtOAc, 3 : 1–2 : 1, v/v)
J5,6a = 2.0 Hz, J6a ,6b = 12.5 Hz, H-6aꢀ), 2.97 (t, 1H, J3
=
ꢀ
ꢀ
ꢀ
ꢀꢀ ꢀꢀ
,4
J4 = 9.0 Hz, H-4ꢀꢀ), 2.82 (dd, 1H, J1,2 = 8.0 Hz, J2,3 = 9.0 Hz,
ꢀꢀ ꢀꢀ
,5
H-2), 1.87 (s, 12H, CH3CO2), 1.38 (d, 3H, J = 6.0 Hz, CH3). 13
C
NMR (75 MHz, D2O) (acetate salt) d 181.3 (CH3CO2), 103.2
(C-1), 102.1 (C-1ꢀꢀ), 96.9 (C-1ꢀ), 81.5, 75.8, 74.9, 73.7, 72.0, 70.9,
70.1, 69.2, 59.4, 57.6 (OCH3), 56.9 (C-2), 56.0 (C-4ꢀꢀ), 54.1 (C-2ꢀ),
40.1 (C-6ꢀ), 23.2 (CH3CO2), 16.8 (CH3).
providing 14 (11.0 mg, 75%). [a]25 +47.8 (c 1.2, CHCl3); 1H
D
NMR (300 MHz, CDCl3): d 7.40–7.20 (m, 10H, aromatics), 5.81
Methyl 3-O-(2ꢀ,6ꢀ-diamino-2ꢀ,6ꢀ-dideoxy-a-D-glucopyranosyl)-4-
O-(4ꢀꢀ -amino-4ꢀꢀ,6ꢀꢀ -dideoxy-b-D-glucopyranosyl)-2,6-diamino-2,6-
dideoxy-b-D-glucopyranoside (17). Trisaccharide 15 (15.0 mg)
was hydrogenated in pyridine (3.0 mL) in the presence of
Pd/C (20 mg) as described in the general procedures section.
The intermediate was further hydrogenated in AcOH and H2O
(10 : 1, v/v, 2.2 mL) in the presence of Pd(OH)2 (20 mg) to give
(d, 1H, J1 ,2 = 3.5 Hz, H-1ꢀ), 4.95–4.85 (m, 3H, PhCH2), 4.63 (d,
ꢀ
ꢀ
ꢀꢀ ꢀꢀ
1H, J2 = 11.5 Hz, PhCH2), 4.60 (d, 1H, J1
= 8.0 Hz, H-1ꢀꢀ),
,2
4.32 (m, 1H, H-5ꢀ), 4.29 (d, 1H, J1,2 = 8.0 Hz, H-1), 4.15 (t, 1H,
J3,4 = J4,5 = 9.5 Hz, H-4), 4.06 (t, 1H, J3 ,4 = J4 ,5 = 9.0 Hz, H-4ꢀ),
ꢀ
ꢀ
ꢀ ꢀ
3.97 (t, 1H, J2
= J3
= 7.5 Hz, H-3ꢀꢀ), 3.74 (t, 1H, J2,3
=
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
,4
,3
J3,4 = 9.0 Hz, H-3), 3.60 (s, 3H, OCH3), 3.58–3.44 (m, 4H, H-3ꢀ,
H-5ꢀꢀ, H-6b, H-6bꢀ), 3.43–3.30 (m, 6H, H-2ꢀ, H-2ꢀꢀ, H-4ꢀꢀ, H-5,
H-6a, H-6aꢀ), 3.12 (dd, 1H, J1,2 = 8.0 Hz, J2,3 = 9.5 Hz, H-2),
1.44 (d, 3H, J = 6.5 Hz, CH3). 13C NMR (75 MHz, CDCl3): d
137.9, 137.8, 128.7, 128.3, 128.2, 128.0, 103.1 (C-1), 101.6 (C-1ꢀꢀ),
96.4 (C-1ꢀ), 79.9, 78.9, 77.4, 75.7, 75.6, 75.5, 75.2 (x2), 75.0, 71.5,
71.1, 67.4, 65.3 (C-4ꢀꢀ), 63.4 (C-2), 60.9 (C-2ꢀ), 57.6 (OCH3), 51.2
(C-6ꢀ), 18.2 (CH3). ESI HRMS: m/z 805.3082 [M + Na+]. Calcd
for C33H42N12O11 805.3096.
1
trisaccharide 17 (6.6 mg): H NMR (D2O, 500 MHz) (acetate
salt): d 5.38 (d, 1H, J1 ,2 = 3.5 Hz, H-1ꢀ), 4.42 (d, 1H, J1
=
ꢀ
ꢀ
ꢀꢀ ꢀꢀ
,2
8.0 Hz, H-1ꢀꢀ), 4.28 (d, 1H, J1,2 = 8.0 Hz, H-1), 4.07 (m, 1H, H-5ꢀ),
3.95–3.70 (m, 3H, H-4, H-4ꢀ, H-5ꢀꢀ), 3.65–3.43 (m, 3H, H-3, H-3ꢀ,
H-6b), 3.51 (s, 3H, OCH3), 3.40–3.28 (m, 5H, H-2ꢀ, H-3ꢀꢀ, H-5,
H-6a, H-6bꢀ), 3.19 (dd, 1H, J5,6a = 2.0 Hz, J6a ,6b = 12.5 Hz,
ꢀ
ꢀ
H-6aꢀ), 3.15 (dd, 1H, J1
= 8.0 Hz, J2
= ꢀ9.8 Hz, H-2ꢀꢀ),
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
,3
,2
= 9.5 Hz, H-4ꢀꢀ), 2.92 (dd, 1H, J1,2
=
ꢀꢀ ꢀꢀ
ꢀꢀ ꢀꢀ
3.01 (t, 1H, J3
= J4
,4
,5
8.0 Hz, J2,3 = 9.5 Hz, H-2), 1.80 (s, 15H, CH3CO2), 1.29
(d, 3H, J = 6.5 Hz, CH3). 13C NMR (75 MHz, D2O) (acetate salt) d
181.3 (CH3CO2), 103.2 (C-1), 102.5 (C-1ꢀꢀ), 97.0 (C-1ꢀ), 81.5, 78.6,
73.6, 71.8, 71.1, 70.7, 70.0 (C-5ꢀ), 69.2, 69.0, 57.7 (OCH3), 56.7
(C-4ꢀ), 55.8 (C-2), 54.0, 40.0 (C-6), 39.8 (C-6ꢀ), 22.7 (CH3CO2),
16.7 (CH3).
Methyl 3-O-(2ꢀ,6ꢀ-diazido-3ꢀ,4ꢀ-di-O-benzyl-2ꢀ,6ꢀ-dideoxy-a-D-
glucopyranosyl)-4-O-(4ꢀꢀ-azido-4ꢀꢀ,6ꢀꢀ-dideoxy-b-D-glucopyranosyl)-
2,6-diazido-2,6-dideoxy-b-D-glucopyranoside (15). A TMSOTf
(5 lL) catalyzed glycosylation of 9 (15 mg, 0.024 mmol) with
6 (15 mg, 0.036 mmol) was performed in CH2Cl2 (2.0 mL) to
afford a trisaccharide (MALDI-TOF: m/z 914.34 [M + Na+])
which was de-O-acetylated as described. The crude material was
purified by silica gel chromatography (hexane–EtOAc, 1 : 1–2 :
Methyl 3-O-(2ꢀ,3ꢀ,5ꢀ-tri-O-benzoyl-b-D-ribofuranosyl)-2-azido-
4,6-O-benzylidene-2-deoxy-b-D-glycopyranoside (18). A TMSOTf
(6 lL) catalyzed glycosylation of 3 (49 mg, 0.160 mmol) with
5 (115 mg, 0.160 mmol) was performed in CH2Cl2 (2.0 mL) as
described in the general procedures section. Chromatography of
the product over silica gel using a mixture of hexane and EtOAc
3, v/v) providing 15 (8.0 mg, 68%). [a]25 +18.3 (c 1.0, CHCl3);
D
1H NMR (300 MHz, CDCl3): d 7.40–7.20 (m, 10H, aromatics),
5.76 (d, 1H, J1 ,2 = 3.5 Hz, H-1ꢀ), 4.95–4.85 (m, 3H, PhCH2), 4.62
ꢀ
ꢀ
(d, 1H, J2 = 11.5 Hz, PhCH2), 4.41 (d, 1H, J1 = 8.0 Hz, H-1ꢀꢀ),
ꢀꢀ ꢀꢀ
,2
4.30 (m, 1H, H-5ꢀ), 4.28 (d, 1H, J1,2 = 8.0 Hz, H-1), 4.10–4.01 (m,
(5 : 1, v/v) as an eluent gave 18 (116 mg, 97%). [a]25 +38.7 (c
2H, H-4, H-4ꢀ), 3.74–3.68 (m, 2H, H-3, H-3ꢀ), 3.60 (s, 3H, OCH3),
3.58–3.46 (m, 3H, H-5ꢀꢀ, H-6b, H-6bꢀ), 3.43–3.29 (m, 6H, H-2ꢀ,
D
1
1.5, CHCl3); H NMR (500 MHz, CDCl3): d 8.20–7.80 (m, 6H,
ꢀ
ꢀ
ꢀ ꢀ
PhCO), 7.60–7.20 (m, 14H, aromatics), 5.80 (t, 1H, J2 ,3 = J3 ,4
=
H-2ꢀꢀ, H-4ꢀꢀ, H-5, H-6a, H-6aꢀ), 3.11 (dd, 1H, J1,2 = 8.0 Hz, J2,3
=
7.2 Hz, H-3ꢀ), 5.62 (s, 1H, PhCH), 5.58 (dd, 1H, J1 ,2 = 1.8 Hz,
ꢀ
ꢀ
9.5 Hz, H-2), 1.46 (d, 3H, J = 6.5 Hz, CH3). 13C NMR (75 MHz,
CDCl3): d 137.9, 137.8, 128.7, 128.3, 128.2, 128.0, 102.8 (C-1),
100.7 (C-1ꢀꢀ), 96.5 (C-1ꢀ), 79.5, 78.7 (C-4), 77.7 (C-4ꢀ), 76.9, 76.7,
75.5, 75.4, 75.0, 74.7, 71.6 (C-5ꢀ), 71.1, 67.5 (C-2), 65.0, 63.1, 57.1
(OCH3), 53.6, 51.0 (C-6ꢀ), 50.7 (C-6), 18.0 (CH3). ESI HRMS:
m/z 830.3174 [M + Na+]. Calcd for C33H41N15O10 830.3161.
ꢀ
ꢀ
ꢀ
ꢀ ꢀ
J2 ,3 = 7.2 Hz, H-2 ), 5.50 (m, 1H, H-3), 5.31 (d, 1H, J1 ,2 = 1.8 Hz,
H-1ꢀ), 4.55 (m, 1H, H-4ꢀ), 4.39 (d, 1H, J1,2 = 7.8 Hz, H-1), 4.37
(m, 1H, H-6a), 4.15 (m, 1H, H-5aꢀ), 3.90–3.64 (m, 3H, H-4, H-
5bꢀ, H-6b), 3.61 (s, 3H, OCH3), 3.59–3.38 (m, 2H, H-2, H-5). 13
C
NMR (75 MHz, CDCl3): d 166.5, 166.2, 165.5 (PhCO), 137.0,
133.4, 133.3, 133.2, 130.3, 130.2, 130.0, 129.6, 128.6, 128.5 (x2),
126.3, 104.1 (C-1), 101.9 (PhCH), 99.0 (C-1ꢀ), 79.3, 76.6, 68.8,
67.9, 67.1, 66.8, 66.2, 61.8, 60.7 (C-2), 57.8 (OCH3). ESI HRMS:
m/z 774.2385 [M + Na+]. Calcd for C40H37N3O12 774.2377.
Methyl 3-O-(2ꢀ,6ꢀ-diamino-2ꢀ,6ꢀ-dideoxy-a-D-glucopyranosyl)-4-
O-(4ꢀꢀ-amino-4ꢀꢀ,6ꢀꢀ-dideoxy-b-D-glucopyranosyl)-2-amino-2-deoxy-
b-D-glucopyranoside (16). Trisaccharide 14 (7.0 mg) was
1334 | Org. Biomol. Chem., 2006, 4, 1328–1337
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The Royal Society of Chemistry 2006
©