Molecules 2007, 12
methoxyphenyl)acrylate (19) as a colourless oil (yield: 66%); IR (cm-1): 3440 (OH), 2924-2854 (CH),
2543
1
3
1769 (C=O), 1700 (C=C), 1260 (C(CH3)2); H-NMR: 9.03 (bs, 1H, OH), 7.56 (d, Jtrans=16.0 Hz, 1H,
H2), 7.35 (s, 1H, H2), 7.20 (d, 3J=7.8 Hz, 1H, H6), 6.98 (d, 3J=7.8 Hz, 1H, H5), 6.55 (d, 3Jtrans=16.0 Hz,
1H, H3), 5.43 (bs, 1H, OH), 4.77-4.76 (m, 1H, H4), 4.43-4.39 (m, 2H), 4.21-4.20 (m, 1H, H6), 4.14-
3.97 (m, 5H), 4.10-4.09 (m, 2H, OCH2), 3.80 (s, 3H, OCH3), 1.64-1.62 (m, 2H, CH2), 1.24 (s, 6H,
13
CH3), 1.23-1.21 (m, 18H, (CH2)9), 0.84-0.82 (m, 3H, CH3); C-NMR: 174.4, 172.3, 167.4, 149.3,
146.5, 144.5, 128.2, 126.6, 123.1, 115.7, 112.8, 111.5, 110.7, 77.7, 76.1, 70.5, 72.0, 70.1, 65.1, 64.6,
53.7, 31.9, 30.4, 29.8, 29.6, 29.5, 29.4, 29.3, 28.7, 26.3, 26.1, 25.9, 22.7, 14.1; MS (EI) m/z: 635 (M+ •,
5), 436 (69), 362 (65), 194 (100).
Synthesis of methyl 2(E)-3-(4-(3-((R)-2-((S)-1,2-dihydroxyethyl)-4-hydroxy-5-oxo-2,5-dihydrofuran-3-
yloxy)-2-hydroxypropoxy)-3-methoxyphenyl)acrylate (20)
To a solution of methyl 2(E)-3-(4-(3-((R)-2-((S)-2,2-dimethyl-1,3-dioxolan-4-yl)-4-hydroxy-5-
oxo-2,5-dihydrofuran-3-yloxy)-2-hydroxypropoxy)-3-methoxyphenyl)acrylate (17, 2.0 g, 4.2 mmol) in
1,4-dioxane (30 mL) was added HCl (12 N, 0.6 mL) and the resulting mixture was stirred at room
temperature for 4 h. The organic layer was neutralized with saturated NaHCO3 solution (100 mL), and
extracted with ethyl acetate (3 x 40 mL), dried (MgSO4), and concentrated in vacuo. The residue was
chromatographed on silica gel (ethyl acetate) to afford 1.3 g of methyl 2(E)-3-(4-(3-((R)-2-((S)-1,2-
dihydroxyethyl)-4-hydroxy-5-oxo-2,5-dihydrofuran-3-yloxy)-2-hydroxypropoxy)-3-methoxyphenyl)-
acrylate (20) as a white solid (yield: 71%); m.p.: 69°C; [α]20 = +21.0 (c 0.5, C2H5OH); IR (cm-1): 3452
D
1
(OH), 2953 (CH), 1765 (C=O), 1692 (C=C), 1259 (C-O); H-NMR: 8.82 (bs, 1H, OH), 7.58 (d,
3
3
3Jtrans=15.9 Hz, 1H, H2), 7.35 (s, 1H, H2), 7.22 (d, J=8.1 Hz, 1H, H6), 7.00 (d, J=8.1 Hz, 1H, H5),
6.56 (d, 3Jtrans=15.9 Hz, 1H, H3), 5.43 (bs, 1H, OH), 4.96-4.78 (m, 2H, H4, H5), 4.43-4.41 (m, 2H, H6),
4.00-3.99 (m, 5H), 3.80 (s, 3H, CO2CH3), 3.70 (s, 3H, OCH3); 13C-NMR: 170.5, 167.0, 150.41 149.2,
144.7, 127.2, 122.9, 119.3, 118.1, 115.4, 112.9, 110.8, 74.6, 71.9, 69.7, 68.6, 67.6, 61.7, 55.7, 51.3.
MS (ESI+) m/z 441 (M++1).
\Synthesis of ethyl 2(E)-3-(4-(3-((R)-2-((S)-1,2-dihydroxyethyl)-4-hydroxy-5-oxo-2,5-dihydrofuran-3-
yloxy)-2-hydroxypropoxy)-3-methoxyphenyl)acrylate (21)
The same procedure as compound 20 starting from ethyl 2(E)-3-(4-(3-((R)-2-((S)-2,2-dimethyl-1,3-
dioxolan-4-yl)-4-hydroxy-5-oxo-2,5-dihydrofuran-3-yloxy)-2-hydroxypropoxy)-3-methoxyphenyl)-
acrylate (18, 0.3 g, 0.5 mmol) was used to prepare 8.6 mg of ethyl 2(E)-3-(4-(3-((R)-2-((S)-1,2-
dihydroxyethyl)-4-hydroxy-5-oxo-2,5-dihydrofuran-3-yloxy)-2-hydroxypropoxy)-3-methoxyphenyl)-
acrylate (21) as a white solid (yield: 61%); m.p.: 68°C; [α]20 = +21.0 (c 0.5, C2H5OH); IR (cm-1): 3419
D
1
(OH), 2936 (CH), 1760 (C=O), 1694 (C=C), 1259 (C-O); H-NMR: 8.83 (bs, 1H, OH), 7.56 (d,
3
3
3Jtrans=15.9 Hz, 1H, H2), 7.34 (s, 1H, H2), 7.20 (d, J=8.0 Hz, 1H, H6), 6.99 (d, J=8.0 Hz, 1H, H5),
3
6.53 (d, Jtrans=15.9 Hz, 1H, H3), 5.44 (bs, 1H, OH), 4.97-4.38 (m, 2H, H4, H5), 4.18-4.00 (m, 5H),
13
3.80 (s, 3H, OCH3), 1.23 (t, J=7.0 Hz, 3H, CH3); C-NMR: 170.9, 166.0, 150.7, 149.6, 144.9, 127.7,
123.2, 119.8, 118.7, 116.2, 113.4, 111.2, 75.0, 72.3, 70.3, 69.0, 67.9, 62.2, 60.2, 56.1, 14.5; MS (ESI+)
m/z 455 (M++1).