7.56-7.47 (m, 5H, Ar-H), 7.46-7.42 (m, 1H, Ar-H), 7.41 – 7.33 (m, 7H, Ar-H), 7.30 (m, 2H,
Ar-H), 6.79 (m, 2H, Ar-H), 6.40 (d, J = 8.0, 1H, H-1), 6.02 (t, J = 9.5, 1H, H-3), 5.78 (t, J =
9.7, 1H, H-4), 4.66 (dd, J = 12.2, 2.9, 1H, H-6b), 4.52 (dd, J = 12.2, 5.0, 1H, H-6a), 4.45 (ddd,
J = 10.0, 5.0, 3.0, 1H, H-5), 3.93 (dd, J = 9.5, 8.0, 1H, H-2), 3.76 (s, 3H, OMe);
13 C NMR (126
MHz, CDCl3): δ 166.13, 165.45, 165.17, 164.38 (each C=O), 164.34 (ArCH=N), 162.07 (ArCOCH3), 133.48, 133.34, 133.00, 132.95, 130.16, 129.93, 129.83, 129.80 (each Ar-CH),
129.70 (Ar-C), 129.52 (Ar-CH), 129.27, 129.10, 128.91 (each Ar-C), 128.37( Ar-CH), 128.33
( Ar-C), 128.26, 128.23, 113.84, (each Ar-CH), 93.99 (C-1), 73.82 (C-3), 73.51 (C-2), 73.07
(C-5), 69.38 (C-4), 63.14 (C-6), 55.29 (OMe); HRMS (ESI): [M+H]+ calcd. for C42H35NO10,
714.2333; found 714.2330; Anal. Calcd for C42H35NO10: C, 70.68; H, 4.94; N, 1.96; Found: C,
71.08; H, 5.09; N, 2.03.
1,3,4,6-Tetra-O-benzoyl-2-deoxy-2-amino-β-D-glucopyranose hydrochloride (4). 5 M HCl
(3.5 m) was added dropwise at reflux temperature to a solution of 3 (9.18 g, 12.8 mmol) in
acetone (50 mL). When a white precipitate was formed after ~10 min the mixture was allowed
to cool to room temperature. The precipitate formed was filtered and washed with successively
with acetone (20 mL) and Et2O (2 x 50 mL), and the solid was crystallized (3 crops) and
subsequently recrystallized from MeOH. After drying under vacuum the title compound (6.86
g after three crops, 85 %) showed mp 179.7-180.9 °C dec. (lit
8 200-201 °C, dec); [α]D = +22.6
(c 1, DMSO);
1 H NMR (500 MHz, DMSO-d6) δ 8.72 (s, 3H, NH3Cl), 8.18-8.13 (m, 2H, ArH), 7.89 (m, 4H, Ar-H), 7.82-7.77 (m, 2H, Ar-H), 7.75-7.70 (m, 1H , Ar-H), 7.60 (m, 5H, ArH), 7.46 (m, 6H, Ar-H), 6.41 (d, J = 8.5, 1H, H-1), 5.96 (t, J = 9.7, 1H, H-3), 5.59 (t, J = 9.6,
1H, H-4), 4.57 (dt, J = 10.1, 3.5, 1H, H-5), 4.47 (m, 2H, H-6), 4.12 (t, J = 9.5, 1H, H-2);
13 CNMR (126 MHz, DMSO-d6): δ 165.72, 165.59, 165.17, 164.26 (C=O), 134.77, 134.26, 134.00,
133.94, 130.63, 129.97, 129.72, 129.69 (each Ar-CH), 129.62, 129.60 (each Ar-C), 129.22,
Ar-H), 6.79 (m, 2H, Ar-H), 6.40 (d, J = 8.0, 1H, H-1), 6.02 (t, J = 9.5, 1H, H-3), 5.78 (t, J =
9.7, 1H, H-4), 4.66 (dd, J = 12.2, 2.9, 1H, H-6b), 4.52 (dd, J = 12.2, 5.0, 1H, H-6a), 4.45 (ddd,
J = 10.0, 5.0, 3.0, 1H, H-5), 3.93 (dd, J = 9.5, 8.0, 1H, H-2), 3.76 (s, 3H, OMe);
13 C NMR (126
MHz, CDCl3): δ 166.13, 165.45, 165.17, 164.38 (each C=O), 164.34 (ArCH=N), 162.07 (ArCOCH3), 133.48, 133.34, 133.00, 132.95, 130.16, 129.93, 129.83, 129.80 (each Ar-CH),
129.70 (Ar-C), 129.52 (Ar-CH), 129.27, 129.10, 128.91 (each Ar-C), 128.37( Ar-CH), 128.33
( Ar-C), 128.26, 128.23, 113.84, (each Ar-CH), 93.99 (C-1), 73.82 (C-3), 73.51 (C-2), 73.07
(C-5), 69.38 (C-4), 63.14 (C-6), 55.29 (OMe); HRMS (ESI): [M+H]+ calcd. for C42H35NO10,
714.2333; found 714.2330; Anal. Calcd for C42H35NO10: C, 70.68; H, 4.94; N, 1.96; Found: C,
71.08; H, 5.09; N, 2.03.
1,3,4,6-Tetra-O-benzoyl-2-deoxy-2-amino-β-D-glucopyranose hydrochloride (4). 5 M HCl
(3.5 m) was added dropwise at reflux temperature to a solution of 3 (9.18 g, 12.8 mmol) in
acetone (50 mL). When a white precipitate was formed after ~10 min the mixture was allowed
to cool to room temperature. The precipitate formed was filtered and washed with successively
with acetone (20 mL) and Et2O (2 x 50 mL), and the solid was crystallized (3 crops) and
subsequently recrystallized from MeOH. After drying under vacuum the title compound (6.86
g after three crops, 85 %) showed mp 179.7-180.9 °C dec. (lit
8 200-201 °C, dec); [α]D = +22.6
(c 1, DMSO);
1 H NMR (500 MHz, DMSO-d6) δ 8.72 (s, 3H, NH3Cl), 8.18-8.13 (m, 2H, ArH), 7.89 (m, 4H, Ar-H), 7.82-7.77 (m, 2H, Ar-H), 7.75-7.70 (m, 1H , Ar-H), 7.60 (m, 5H, ArH), 7.46 (m, 6H, Ar-H), 6.41 (d, J = 8.5, 1H, H-1), 5.96 (t, J = 9.7, 1H, H-3), 5.59 (t, J = 9.6,
1H, H-4), 4.57 (dt, J = 10.1, 3.5, 1H, H-5), 4.47 (m, 2H, H-6), 4.12 (t, J = 9.5, 1H, H-2);
13 CNMR (126 MHz, DMSO-d6): δ 165.72, 165.59, 165.17, 164.26 (C=O), 134.77, 134.26, 134.00,
133.94, 130.63, 129.97, 129.72, 129.69 (each Ar-CH), 129.62, 129.60 (each Ar-C), 129.22,