Molecules 2019, 24, 4340
15 of 27
2 d. By the same procedure previously described for the preparation of compound 17, compound 24
(1.2 g, 92%) was obtained as a colorless amorphous oil. [α]2D0 80.8 (c 1.00, CHCl3); 1
NMR (CDCl3
600 MHz) 7.41–7.14 (m, 44H), 5.58 (t, J = 9.5 Hz, 1H), 5.31 (t, J = 9.8 Hz, 1H), 5.09–5.00 (m, 12H),
4.54, 4.48 (ABq, J = 12.2 Hz, 2H), 4.52, 4.47 (ABq, J = 12.0 Hz, 2H), 4.19 (dd, J = 11.5, 5.3 Hz, 1H), 3.79
=
−
H
,
δ
(
(
td, J = 9.9, 5.2 Hz, 1H), 3.73 (m, 1H), 3.59 (dd, J = 10.7, 2.4 Hz, 1H), 3.51 (dd, J = 10.8, 5.3 Hz, 1H), 3.46
t, J = 11.0 Hz, 1H); 13
C
NMR (CDCl3, 150 MHz) 165.62, 165.18, 152.43, 142.67, 142.53, 137.56, 137.48,
δ
137.43, 137.39, 136.57, 136.56, 128.49, 128.41, 128.38, 128.36, 128.27, 128.16, 127.98, 127.89, 127.87, 127.84,
127.65, 127.55, 124.67, 124.20, 109.15, 77.99, 76.35, 75.22, 75.10, 75.08, 73.70, 72.96, 71.12, 70.07, 69.06,
68.30; HRMS (ESI, m/z): [M + Na]+, calcd for [C76H68O13 Na]+: 1211.4558; found 1211.4558.
1,5-Anhydro-2,4-bis-O-benzyl-3,6-bis-O-(30,40,50-tribenzyloxybenzoyl)-d-glucitol (25); Compound
9
(0.52 mg, 1.5 mmol), compound 16 (2.0 g, 4.5 mmol), 2-chloro-1-methylpyridinium iodide (1.2 g,
4.5 mmol), DMAP (0.55 g, 4.5 mmol), TEA (1.2 mL, 9.0 mmol) in 20 mL of DCM was stirred at rt for
2 d. By the same procedure previously described for the preparation of compound 17, compound
25 (1.6 g, 91%) was obtained as a colorless amorphous oil. [α]2D0 = +16.1 (c 1.00, CHCl3); 1H NMR
(CDCl3, 600 MHz) δ 7.43–7.24 (m, 34H), 7.18–7.05 (m, 10H), 5.50 (t, J = 9.3 Hz, 1H), 5.19–5.08 (m, 12H),
4.56, 4.43 (ABq, J = 12.4 Hz, 2H), 4.55 (dd, J = 12.0 Hz, 2.0 Hz, 1H), 4.45 (dd, J = 12.0, 5.5 Hz, 1H) 4.41
(s, 2H), 4.11 (dd, J = 11.3, 5.2 Hz, 1H), 3.67–3.62 (m, 2H), 3.54 (t, J = 9.5 Hz, 1H), 3.36 (t, J = 11.0 Hz, 1H);
13C NMR (CDCl3, 150 MHz)
δ 165.84, 165.22, 152.49, 142.66, 137.65, 137.31, 136.99, 136.59, 128.56, 128.36,
128.22, 128.16, 128.05, 127.94, 127.83, 127.52, 127.47, 124.96, 124.88, 109.54, 109.51, 78.19, 77.87, 76.42,
75.26, 75.13, 74.68, 72.63, 71.32, 67.97, 63.91; HRMS (ESI, m/z): [M + Na]+, calcd for [C76H68O13 Na]+
:
1211.4558; found 1211.4557.
1,5-Anhydro-2,3-bis-O-benzyl-4,6-bis-O-(30,40,50-tribenzyloxybenzoyl)-d-glucitol (26); Compound
5
(0.34 g, 1.0 mmol), compound 16 (1.3 g, 3.0 mmol), 2-chloro-1-methylpyridinium iodide (0.77 g,
3.0 mmol), DMAP (0.37 g, 3.0 mmol), TEA (0.83 mL, 6.0 mmol) in 20 mL of DCM was stirred at rt for
2 d. By the same procedure previously described for the preparation of compound 17, compound 26
(1.0 g, 87%) was obtained as a colorless amorphous oil. [α]2D0 = +13.7 (c 1.00, CHCl3); 1
H NMR (CDCl3,
600 MHz) δ 7.45–7.21 (m, 39H), 7.12–7.03 (m, 5H), 5.32 (t, J = 9.5 Hz, 1H), 5.15–5.08 (m, 8H), 5.03–5.01
(m, 4H), 4.79, 4.58 (ABq, J = 11.5, 2H), 4.76, 4.66 (ABq, J = 11.5 Hz, 2H), 4.63 (dd, J = 12.0, 2.8 Hz, 1H),
4.12 (dd, J = 12.2, 5.3 Hz, 1H), 4.07 (dd, J = 11.5, 5.0 Hz, 1H), 3.70–3.68 (m, 2H), 3.70 (t, J = 8.9 Hz, 1H),
3.30 (t, J = 10.8 Hz, 1H); 13
C NMR (CDCl3, 150 MHz) δ 165.80, 164.76, 152.48, 152.44, 142.77, 142.42,
137.98, 137.91, 137.47, 137.37, 136.73, 136.56, 128.53, 128.50, 128.47, 128.20, 128.17, 128.07, 128.03, 128.01,
127.94, 127.84, 127.60, 127.53, 124.75, 124.54, 109.40, 109.14, 82.95, 78.22, 76.56, 75.15, 75.08, 73.47, 71.24,
71.06, 70.96, 68.32, 63.44; HRMS (ESI, m/z): [M + Na]+, calcd for [C76H68O13 Na]+: 1211.4558; found
1211.4553.
1,5-Anhydro-2,3,4-tris-O-(30,40,50-tribenzyloxybenzoyl)-6-O-benzyl-d-glucitol (27); Compound 12
(180 mg, 0.70 mmol), compound 16 (1.4 g, 3.2 mmol), 2-chloro-1-methylpyridinium iodide (0.82 g,
3.2 mmol), DMAP (0.39 g, 3.2 mmol), TEA (0.89 mL, 6.4 mmol) in 20 mL of DCM was stirred at rt for
2 d. By the same procedure previously described for the preparation of compound 17, compound
27 (0.94 g, 91%) was obtained as a colorless amorphous oil. [α]D20
CDCl3, 600 MHz)
=
−
4.9 (c 0.65, CHCl3); 1H NMR
7.43–7.16 (m, 56H), 5.82 (t, J = 9.6 Hz, 1H), 5.55 (t, J = 10.0 Hz, 1H), 5.29 (td, J = 10.0,
(
δ
5.5 Hz, 1H), 5.13–4.96 (m, 14H), 4.90 (s, 4H), 4.58, 4.53 (ABq, J = 12.0, 2H), (dd, J = 10.2, 5.6 Hz, 1H),
3.88–3.84 (m, 1H), 3.67 (dd, J = 11.0, 2.4 Hz, 1H), 3.61 (dd, J = 10.8, 5.3 Hz, 1H), 3.57 (t, J = 10.8 Hz,
1H) 13
C NMR (CDCl3, 150 MHz) δ 165.92, 165.17, 165.02, 152.54, 152.50, 142.88, 142.82, 142.71, 137.44,
137.34, 136.49, 136.45, 136.36, 128.55, 128.51, 128.39, 128.32, 128.27, 128.17, 128.15, 128.10, 128.06, 128.02,
127.95, 127.92, 127.89, 127.81, 127.72, 127.56, 127.52, 124.08, 124.03, 109.20, 109.11, 109.02, 78.36, 75.12,
75.09, 75.07, 74.65, 73.77, 71.18, 71.10, 71.02, 70.75, 69.71, 69.00, 67.26; HRMS (ESI, m/z): [M + Na]+
calcd for [C97H84O17 Na]+: 1543.5606; found 1543.5601.
,
1,5-Anhydro-2,3,6-tris-O-(30,40,50-tribenzyloxybenzoyl)-4-O-benzyl-d-glucitol (28); Compound
8 (0.38 mg,
1.5 mmol), compound 16 (3.0 g, mmol), 2-chloro-1-methylpyridinium iodide (1.8 g, 7.0 mmol), DMAP
(0.12 g, 1.0 mmol), TEA (1.9 mL, 14 mmol) in 30 mL of DCM was stirred at rt for 1 d. By the same procedure