Molecules 2021, 26, 2541
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(500 MHz):
δ
1.36 (s, 3H, CH3), 1.56 (s, 3H, CH3), 3.06 (dd, J1a,1b = 11.9 Hz, J1a,2 = 1.9 Hz,
1H, H1a), 3.33 (dd, J1b,1a = 11.9 Hz, J1b,2 = 5.1 Hz, 1H, H1b), 3.83 (m, 1H, H4), 3.99 (dd,
J5a,5b = 9.9 Hz, J5a,4 = 7.8 Hz, 1H, H5a), 4.16 (dd, J5b,5a = 9.9 Hz, J5b,4 = 5.2 Hz, 1H, H5b), 4.91
(dd, J3,2 = 5.6 Hz, J3,4 = 1.7 Hz, 1H, H3), 5.05 (dt, J2,3 = 5.6 Hz, J2,1b = 5.3 Hz, J2,1a = 1.9 Hz,
1H, H2), 6.77 (d, J = 9.2 Hz, 2H, Ar), 6.80 (d, J = 9.3 Hz, 2H, Ar); 13C NMR (125 MHz):
δ 24.7,
26.7, 30.2, 47.2, 71.3, 85.2, 87.7, 110.6, 115.9, 116.1, 150.0, 152.5. Anal. Calcd for C14H18O4Se:
C, 51.07; H, 5.51. Found: C, 51.10; H, 5.50.
Under the above conditions, (E)-5-((3-(3,4-dihydroxyphenyl)acryloyl)oxy)-1,4-deoxy-2,3-O-
isopropylidene-4-seleno-D-ribose (13) was obtained as oil (70%) starting from the compound
7
and caffeic acid: 1H NMR (500 MHz):
δ
1.34 (s, 3H, CH3), 1.54 (s, 3H, CH3), 3.06 (dd,
J1a,1b = 12.1 Hz, J1a,2 = 1.7 Hz, 1H, H1a), 3.26 (dd, J1b,1a = 12.1 Hz, J1b,2 = 4.9 Hz, 1H, H1b),
3.76 (m, 1H, H4), 4.26 (dd, J5a,5b = 11.6 Hz, J5a,4 = 8.9 Hz, 1H, H5a), 4.37 (dd, J5b,5a = 11.6 Hz,
J5b,4 = 5.8 Hz, 1H, H5b), 4.77 (dd, J3,2 = 5.5 Hz, J3,4 = 1.6 Hz, 1H, H3), 5.03 (ddd, J2,3 = 5.7 Hz,
J2,1b = 5.0 Hz, J2,1a = 2.0 Hz, 1H, H2), 6.00 (brs, 2H, OH), 6.24 (d, J = 15.9 Hz, 1H, H20),
6.87 (d, J = 8.2 Hz, 1H, H80), 7.00 (dd, J = 8.2 Hz, J = 1.5 Hz, 1H, H90), 7.07 (d, J = 1.5 Hz,
1H, H50), 7.58 (d, J = 15.9 Hz, 1H, H30); 13C NMR (125 MHz):
δ 24.7, 26.7, 29.7, 46.6, 65.7,
85.0, 87.3, 110.9, 114.5, 115.1, 115.6, 122.7, 127.6, 143.8, 145.5, 146.3, 167.0. Anal. Calcd for
C17H20O6Se: C, 51.14; H, 5.05. Found: C, 51.19; H, 5.03.
Under the above conditions, (E)-5-((3-(4-hydroxy-3-methoxyphenyl)acryloyl)oxy)-1,4-deoxy-2,3-
O-isopropylidene-4-seleno-D-ribose (14) was obtained as oil (68%) starting from the compound
1
7
and ferulic acid: H NMR (500 MHz, acetone-d6):
δ
1.30 (s, 3H, CH3), 1.46 (s, 3H, CH3),
2.99 (dd, J1a,1b = 11.9 Hz, J1a,2 = 1.3 Hz, 1H, H1a), 3.37 (dd, J1b,1a = 11.9 Hz, J1b,2 = 4.9 Hz,
1H, H1b), 3.76 (ddd, J4,5a = 8.7 Hz, J4,5b = 7.4 Hz, J4,3 = 1.3 Hz, 1H, H4), 3.95 (s, 3H, CH3),
4.26 (dd, J5a,5b = 11.4 Hz, J5a,4 = 8.8 Hz, 1H, H5a), 4.36 (dd, J5b,5a = 11.4 Hz, J5b,4 = 6.8 Hz,
1H, H5b), 4.86 (dd, J3,2 = 5.8 Hz, J3,4 = 1.5 Hz, 1H0, H3), 5.11 (ddd, J2,3 = 6.1, J2,1b = 5.9 Hz,
0
J2,1a = 1.9 Hz, 1H, H2), 6.46 (d, J = 16.0 Hz, 1H, H2 ), 6.90 (dd, J = 8.0 Hz, 1H, H8 ), 7.18 (dd,
J = 8.5 Hz, J = 1.9 Hz, 1H, H90), 7.39 (d, J = 1.5 Hz, 1H, H50), 7.66 (d, J = 16.0 Hz, 1H, H30);
13C NMR (125 MHz):
δ 24.7, 26.7, 29.3, 46.7, 56.0, 65.6, 85.0, 87.3, 109.4, 110.8, 114.8, 114.8,
123.3, 126.8, 145.7, 146.8, 148.2, 166.9. Anal. Calcd for C18H22O6Se: C, 52.31; H, 5.37. Found:
C, 52.25; H, 5.43.
Under the above conditions, 5-(4-((1E,6E)-7-(4-hydroxy-3-methoxyphenyl)-3,5-dioxohepta-1,6-
dien-1-yl)-2-methoxyphenoxy)-1,4-deoxy-2,3-O-isopropylidene-4-seleno-D-ribose (15) was obtained
as oil (30%) starting from the compound
7 δ 1.36 (s,
and curcumin: 1H NMR (400 MHz):
3H, CH3), 1.57 (s, 3H, CH3), 3.04 (dd, J1a,1b = 12.0 Hz, J1a,2 = 1.9 Hz, 1H, H1a), 3.55 (dd,
J1b,1a = 12.0 Hz, J1b,2 = 5.0 Hz, 1H, H1b), 3.93–3.86 (m, 4H, H4 and CH3), 3.96 (s, 3H, CH3),
4.16 (dd, J5a,5b = 9.7 Hz, J5a,4 = 8.0 Hz, 1H, H5a), 4.33 (dd, J5b,5a = 9.7 Hz, J5b,4 = 5.2 Hz, 1H,
H5b), 4.95 (dd, J3,2 = 5.6 Hz, J3,4 = 1.8 Hz, 1H, H3), 5.11 (ddd, J2,3 = 5.6 Hz, J2,1b = 5.0 Hz,
J2,1a = 1.9 Hz, 1H, H2), 5.82 (m, 2H, H100), 5.98 (bs, 1H, OH), 6.52–6.46 (m, 2H, H80 and
H1200), 6.84 (d, J = 8.3 Hz, 1H, H60), 6.94 (d, J = 8.3 Hz,01H, H180), 7.05 (d, J = 1.7 Hz, 1H,
0
0
0
H15 ), 7.07 (d, J = 1.9 Hz, 1H, H3 ), 7.14–7.09 (m, 2H, H5 and H19 ), 7.65–7.561 (m, 2H, H7
and H130); 13C NMR (125 MHz):
δ 24.6, 26.7, 31.1, 47.1, 56.0, 72.1, 85.6, 88.2, 101.2, 109.6,
110.4, 113.1, 114.8, 121.8, 122.3, 122.9, 129.0, 140.2, 140.6, 146.8, 147.9, 149.7, 182.9, 183.6.
Anal. Calcd for C29H32O8Se: C, 59.29; H, 5.49. Found: C, 59.19; H, 5.55.
Removal of the O-isopropylidene group. Typical Procedure: A solution (3.3 mL) of CH3COOH
/H2O (8:2, v/v) was added to compound 12 (0.329 g, 1.0 mmol). The mixture was stirred at
80 ◦C for 2 h. Then, the solvent was evaporated under reduced pressure; next, the organic
layer was washed with diethylether. The crude residue was purified to afford compound
1
12a as an amorphus solid (0.205 g, 0.8 mmol, 71%). H NMR (400 MHz, acetone-d6):
δ 2.82
(dd, J1a,1b = 10.0 Hz, J1a,2 = 5.1 Hz, 1H, H1a), 3.02 (dd, J1b,1a = 10.0 Hz, J1b,2 = 5.0 Hz, 1H,
H1b), 3.77 (m, 1H, H4), 3.99 (dd, J5a,5b = 9.7 Hz, J5a,4 = 8.3 Hz, 1H, H5a), 4.10 (m, 1H, H3),
4.35 (dd, J5b,5a = 9.7 Hz, J5b,4 = 5.9 Hz, 1H, H5b), 4.40 (m, 1H, H2), 6.75 (d, J = 9.2 Hz, 2H,
Ar), 6.79 (d, J = 9.2 Hz, 2H, Ar); 13C NMR (100 MHz, acetone-d6):
δ 23.9, 42.6, 72.4, 76.0,