Molecules 2011, 16
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4-Methoxycinnamyl 6-trityl-2,3,4-tri-O-benzoyl-β-D-glucopyranoside (18b). Prepared according to the
synthetic method used for the preparation of 18a from 17b (5.7 g, 10 mmol). Yield: 7.93 g (90%). m.p.
88–90 °C; [α]2D5 +21.5 ( c 1.0, CDCl3); H-NMR (600 MHz, DMSO-d6): δ 7.90–7.10 (m, 32H, Ar-H ×
1
32), 6.82 (d, 2H, J = 9.0 Hz, Ar-H × 2), 6.51 (d, 1H, J = 16.2 Hz, =CH), 6.17 (dt, 1H, J = 16.2, 5.4 Hz,
=CH), 5.90 (t, 1H, J = 9.6 Hz), 5.70 (t, 1H, J = 9.6 Hz), 5.47 (t, 1H, J = 9.0 Hz), 5.24 (d, 1H,
J = 7.8 Hz, H-1), 4.51 (dd, 1H, J = 5.4, 13.2 Hz, =CH-CH2), 4.42 (dd, 1H, J = 6.0, 13.2 Hz, =CH-
CH2), 4.26 (dt, 1H, J = 2.4, 9.6 Hz), 3.33 (d, 1H, J = 9.0 Hz), 3.03 (dd, 1H, J = 3.6, 10.2 Hz). 13C-
NMR (75 MHz, DMSO-d6): δ 165.3 (PhCO-), 164.9 (PhCO-), 164.5 (PhCO-), 159.0 (2C, 2Ar-C),
143.5 (3C, 3Ar-C), 133.7 (3C, 3Ar-C), 131.8 (3C, 3Ar-C), 129.3 (2C, 2Ar-C), 129.2 (3C, 3Ar-C),
128.9 (3C, 3Ar-C), 128.8 (3C, 3Ar-C), 128.6 (=CH), 128.2 (6C, 6Ar-C), 127.9 (3C, 3Ar-C), 127.7
(3C, 3Ar-C), 127.0 (3C, 3Ar-C), 122.9 (=CH), 114.0 (2C, 2Ar-C), 99.2 (C-1), 86.0 (Ph3C), 73.7 (C-3),
72.3 (2C, C-5, 2), 69.1 (2C, C-4, =C-CH2), 61.7 (C-6), 55.1 (OCH3). HRMS (ESI-TOF): calcd. for
C56H49O10 (M+H)+ 881.3320; found 881.3347.
Cinnamyl 2,3,4-tri-O-benzoyl-β-D-glucopyranoside (19a). Cinnamyl 6-trityl-2,3,4-tri-O-benzoyl-β-D-
glucopyranoside (18b, 5.0 g, 5.9 mol) was dissolved in CH2Cl2 (30 mL) followed by the addition of
90% aq TFA (3.0 mL) and the solution was allowed to stir for 30 min at room temperature. Then the
solution was poured into a separating funnel and washed successively with water (50 mL), saturated
NaHCO3 (2 × 50 mL) and brine (50 mL). The organic layer was collected, dried (Na2SO4) and filtered.
The filtrate was evaporated and the resulting crude material was purified by silica gel chromatography
using petroleum-ethyl acetate (3:1) as eluent, affording pure compound (3.0 g, 84%) as a light yellow
solid. m.p. 108–110 °C; [α]2D5 +2.9 (c 1.0, CDCl3);1H-NMR (600 MHz, DMSO-d6): δ 7.87–7.15 (m,
20H, Ar-H × 20), 6.51 (d, 1H, J = 16.2 Hz, =CH), 6.23 (dt, 1H, J = 5.4, 16.2 Hz, =CH), 5.93 (t, 1H,
J = 9.6 Hz), 5.49 (d, 1H, J = 9.0 Hz), 5.36 (d, 1H, J = 9.0 Hz), 5.18 (d, 1H, J = 7.8 Hz), 5.06 (s, 1H,
OH), 4.48 (dd, 1H, J = 5.4, 13.2 Hz, =CH-CH2), 4.32 (dd, 1H, J = 6.0, 13.8 Hz, =CH-CH2), 4.09 (m,
1H), 3.66 (m, 2H), 3.06 (dd, 1H, J = 3.0, 10.2 Hz). 13C-NMR (75 MHz, DMSO-d6): δ 165.4 (PhCO-),
165.0 (2C, 2PhCO-), 136.3 (Ar-C), 133.9 (3C, 3Ar-C), 131.8 (=CH), 129.4 (3C, 3Ar-C), 129.2 (2C,
2Ar-C), 129.0 (3C, 3Ar-C), 128.9 (2C, 2Ar-C), 128.7 (3C, 3Ar-C), 127.9 (=CH), 126.4 (3C, 3Ar-C),
125.5 (Ar-C), 99.3 (C-1), 74.2 (C-3), 73.9 (C-5), 72.3 (C-2), 69.6 (C-4), 69.2 (=C-CH2), 60.4 (C-6).
HRMS (ESI-TOF): calcd. for C37H33O11 (M+HCOO)– 653.2023; found 653.2028.
4-Methoxycinnamyl 2,3,4-tri-O-benzoyl-β-D-glucopyranoside (19b). Prepared according to synthetic
method described for preparation of 19a from 18b (6.0 g, 6.8 mmol). Yield: 3.73 g (86%). m.p.
125–127 °C; [α]2D5 +6.8 (c 1.0, CDCl3); 1H-NMR (600 MHz, CDCl3): δ 8.10-7.10 (m, 17H, Ar-H × 17),
6.80 (d, 2H, J = 9.0 Hz, Ar-H × 2), 6.49 (d, 1H, J = 15.6 Hz, =CH), 6.00 (dt, 1H, J = 6.0, 15.0 Hz,
=CH), 5.93 (t, 1H, J = 9.6 Hz), 5.55 (t, 1H, J = 9.0 Hz), 5.51 (t, 1H, J = 9.0 Hz), 4.94 (d, 1H,
J = 7.8 Hz, H-1), 4.51 (dd, 1H, J = 5.4, 13.2 Hz, =CH-CH2), 4.34 (dd, 1H, J = 6.0, 13.8 Hz, =CH-
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CH2), 3.87 (m, 1H), 3.79 (s, 3H, OCH3), 3.82–3.78 (m, 2H), 3.48 (s, 1H, -OH). C-NMR (75 MHz,
CDCl3): δ 166.0 (PhCO-), 165.8 (PhCO-), 165.1 (PhCO-), 159.3 (Ar-C), 133.6 (Ar-C), 133.2 (Ar-C),
132.8 (Ar-C), 130.1 (2C, 2Ar-C), 129.8 (2C, 2Ar-C), 129.7 (2C, 2Ar-C), 129.6 (2C, 2Ar-C), 129.2
(Ar-C), 128.8 (3C, 3Ar-C), 128.2 (2C, 2Ar-C), 127.8 (2C, 2Ar-C), 127.2 (2C, 2Ar-C), 126.9 (Ar-C),
122.1 (Ar-C), 113.9 (2C, 2Ar-C), 99.6 (C-1), 74.6 (C-3), 72.7 (C-5), 71.8 (C-2), 70.1 (C-4), 69.5