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F. Cateni et al. / Bioorg. Med. Chem. 15 (2007) 815–826
(br s, 2H, H2-60), 3.89 (br d, 1H, J = 10.6 Hz, Hb-3), 4.07,
4.14 (dd, 1H, J = 12.0, 6.6 Hz, Ha-1), 4.29 (d, 1H,
J = 7.8 Hz, H-10), 4.34 (br d, 1H, J = 12.0 Hz, Hb-1),
5.23 (br s, 1H, H-2), 5.30–5.38 (m, 8H, 4· CH@CH).
13C NMR (100 MHz, CDCl3): d 173.8, 173.4 (COO),
130.5, 130.4, 128.4, 128.3 (CH@CH), 103.5 (C-10), 76.7
(C-40), 76.1 (C-50), 73.5 (C-20), 70.5 (C-2), 69.7 (C-30),
68.6 (C-3), 63.3, 63.2 (C-1), 61.7 (C-60), 33.8, 33.7
(COCH2), 30.3–21.1 (CH2 aliph.), 27.5 (CH2CH@CH),
26.0 (@CHCH2CH@), 25.5, 25.4 (COCH2CH2), 14.4
(CH3). ESI-MS: m/z = 802 (M+Na, 100%)+.
(dd, 1H, J = 10.7, 6.4 Hz, Ha-3), 3.80 (br s, 2H, H2-60),
3.89 (br d, 1H, J = 10.5 Hz, Hb-3), 4.07, 4.14 (dd, 1H,
J = 12.0, 6.6 Hz, Ha-1), 4.29 (d, 1H, J = 7.7 Hz, H-10),
4.34 (br d, 1H, J = 12.0 Hz, Hb-1), 5.23 (br s, 1H, H-
2), 5.20–5.40 (m, 4H, 2· CH@CH). 13C NMR
(100 MHz, CDCl3): d 173.5, 173.2 (COO), 130.6,
130.4, 128.4, 128.3 (CH@CH), 103.3 (C-10), 76.5 (C-
40), 76.3 (C-50), 73.8 (C-20), 70.6, 70.5 (C-2), 69.9 (C-
30), 68.5 (C-3), 63.3, 63.2 (C-1), 61.8 (C-60), 34.3, 34.1
(COCH2), 32.4–23.2 (CH2 aliph.), 27.6 (CH2CH@CH),
26.0 (@CHCH2CH@), 25.3, 25.2 (COCH2CH2), 14.7
(CH3). ESI-MS: m/z = 666 (M+Na, 100%)+.
4.8.8. 1,2-O-Dilinolenoyl-3-O-(b-D-glucopyranosyl)-rac-glyc-
erol (9h). Yield: 70%. Rf = 0.50 (CH2Cl2/MeOH/10:1,
v:v). H NMR (400 MHz, CDCl3): d 0.97 (br t, 6H,
4.8.11. 1-O-Caprylyl-2-O-linolenoyl-3-O-(b-D-glucopyrano-
syl)-rac-glycerol (13c). Yield: 69%. Rf = 0.50 (CH2 Cl2/
MeOH/10:1, v:v). H NMR (400 MHz, CDCl3): d 0.96
1
1
J = 6.8 Hz, CH3 term.), 1.23 (br s, 16H, CH2 aliph.),
1.54 (br t, 4H, COCH2CH2), 2.10 (br, 8H, 4·
CH2CH@CH), 2.35 (br t, 4H, J = 6.9 Hz, COCH2),
2.90 (br t, 8H, J = 5.6 Hz, 4· @CHCH2CH@), 3.29 (m,
1H, H-50), 3.33 (m, 1H, H-20), 3.57 (m, 1H, H-40), 3.60
(m, 1H, H-30), 3.63, 3.66 (dd, 1H, J = 10.6, 6.3 Hz, Ha-
3), 3.79 (br s, 2H, H2-60), 3.87 (br d, 1H, J = 10.6 Hz,
Hb-3), 4.09, 4.13 (dd, 1H, J = 11.9, 6.7 Hz, Ha-1), 4.28
(d, 1H, J = 7.7 Hz, H-10), 4.38 (br d, 1H, J = 12.0 Hz,
Hb-1), 5.22 (br s, 1H, H-2), 5.30–5.41 (m, 12H, 6·
CH@CH). 13C NMR (100 MHz, CDCl3): d 173.8,
173.4 (COO), 132.2, 130.4, 130.1, 128.6, 128.1, 127.5
(CH@CH), 103.5 (C-10), 76.7 (C-40), 76.1 (C-50), 73.6
(C-20), 70.5 (C-2), 70.0 (C-30), 68.7 (C-3), 63.2, 63.1 (C-
1), 61.8 (C-60), 34.3, 34.1 (COCH2), 30.3–21.1 (CH2
aliph.), 27.7, 27.6, 27.5 (CH2CH@CH), 26.1, 26.0
(@CHCH2CH@), 25.5, 25.4 (COCH2CH2), 14.7 (CH3).
ESI-MS: m/z = 798 (M+Na, 100%)+.
(br t, 6H, J = 6.8 Hz, CH3 term.), 1.25 (br s, 16H, CH2
aliph.), 1.57 (br t, 4H, COCH2CH2), 2.10 (br, 4H, 2·
CH2CH@CH), 2.31 (br t, 4H, J = 7.0 Hz, COCH2),
2.90 (br t, 4H, J = 5.5 Hz, 2· @CHCH2CH@), 3.29 (m,
1H, H-50), 3.34 (m, 1H, H-20), 3.56 (m, 1H, H-40), 3.57
(m, 1H, H-30), 3.62, 3.65 (dd, 1H, J = 10.7, 6.4 Hz, Ha-
3), 3.80 (br s, 2H, H2-60), 3.85 (br d, 1H, J = 10.5 Hz,
Hb-3), 4.07, 4.13 (dd, 1H, J = 11.9, 6.6 Hz, Ha-1), 4.28
(d, 1H, J = 7.7 Hz, H-10), 4.35 (br d, 1H, J = 10.5 Hz,
Hb-1), 5.22 (br s, 1H, H-2), 5.22–5.39 (m, 6H, 3·
CH@CH). 13C NMR (100 MHz, CDCl3): d 173.6,
173.5 (COO), 132.3, 130.4, 130.2, 128.5, 128.0, 127.6
(CH@CH), 103.3 (C-10), 76.5 (C-40), 76.3 (C-50), 73.7
(C-20), 70.6 (C-2), 69.8 (C-30), 68.6 (C-3), 63.1, 62.9 (C-
1), 62.0 (C-60), 34.3, 34.2 (COCH2), 32.3–23.1 (CH2
aliph.), 27.5, 27.6, 27.7 (CH2CH@CH), 26.2, 26.0
(@CHCH2CH@), 25.5, 25.4 (COCH2CH2), 14.8 (CH3).
ESI-MS: m/z = 662 (M+Na, 100%)+.
4.8.9. 1-O-Caprylyl-2-O-oleoyl-3-O-(b-D-glucopyranosyl)-
rac-glycerol (13a). Yield: 71%. Rf = 0.49 (CH2Cl2/
MeOH/10:1, v:v). H NMR (400 MHz, CDCl3): d 0.95
4.8.12. 1-O-Caprinyl-2-O-oleoyl-3-O-(b-D-glucopyranosyl)-
rac-glycerol (14a). Yield: 75%. Rf = 0.50 (CH2Cl2/
MeOH/10:1, v:v). H NMR (400 MHz, CDCl3): d 0.94
1
1
(br t, 6H, J = 6.8 Hz, CH3 term.), 1.23 (br s, 28H,
CH2 aliph.), 1.56 (br t, 4H, COCH2CH2), 1.99 (br,
4H, 2· CH2CH@CH), 2.39 (br t, 4H, J = 7.0 Hz,
COCH2), 3.28 (m, 1H, H-50), 3.35 (m, 1H, H-20), 3.54
(m, 1H, H-40), 3.59 (m, 1H, H-30), 3.62, 3.65 (dd, 1H,
J = 10.7, 6.4 Hz, Ha-3), 3.80 (br s, 2H, H2-60), 3.88 (br
d, 1H, J = 10.6 Hz, Hb-3), 4.08, 4.15 (dd, 1H, J = 12.0,
6.7 Hz, Ha-1), 4.27 (d, 1H, J = 7.5 Hz, H-10), 4.35 (br
d, 1H, J = 12.1 Hz, Hb-1), 5.24 (br s, 1H, H-2), 5.20–
5.40 (m, 2H, CH@CH). 13C NMR (100 MHz, CDCl3):
d 174.2, 174.1 (COO), 130.4, 130.1 (CH=CH), 103.7
(C-10), 76.5 (C-40), 76.3 (C-50), 73.7 (C-20), 70.6, 70.5
(C-2), 70.0 (C-30), 68.5 (C-3), 63.0, 62.9 (C-1), 61.8 (C-
60), 34.6, 34.5 (COCH2), 32.3–23.2 (CH2 aliph.), 27.6,
27.5 (CH2CH@CH), 25.3, 25.2 (COCH2CH2), 14.5
(CH3). ESI-MS: m/z = 668 (M+Na, 100%)+.
(br t, 6H, J = 6.8 Hz, CH3 term.), 1.24 (br s, 32H,
CH2 aliph.), 1.55 (br t, 4H, COCH2CH2), 1.99 (br,
4H, 2· CH2CH@CH), 2.40 (br t, 4H, J = 6.9 Hz,
COCH2), 3.29 (m, 1H, H-50), 3.32 (m, 1H, H-20), 3.54
(m, 1H, H-40), 3.60 (m, 1H, H-30), 3.62, 3.65 (dd, 1H,
J = 10.7, 6.4 Hz, Ha-3), 3.79 (br s, 2H, H2-60), 3.85 (br
d, 1H, J = 10.5 Hz, Hb-3), 4.08, 4.12 (dd, 1H, J = 12.0,
6.7 Hz, Ha-1), 4.27 (d, 1H, J = 7.8 Hz, H-10), 4.38 (br
d, 1H, J = 10.4 Hz, Hb-1), 5.23 (br s, 1H, H-2), 5.20–
5.40 (m, 2H, CH@CH). 13C NMR (100 MHz, CDCl3):
d 173.5, 173.4 (COO), 130.3, 130.2 (CH@CH), 103.2
(C-10), 76.6 (C-40), 76.2 (C-50), 73.8 (C-20), 70.5, 70.4
(C-2), 69.7 (C-30), 68.4 (C-3), 63.3, 63.2 (C-1), 61.9 (C-
60), 34.1, 33.9 (COCH2), 32.3–23.0 (CH2 aliph.), 27.6,
27.5 (CH2CH@CH), 25.5, 25.4 (COCH2CH2), 14.5
(CH3). ESI-MS: m/z = 696 (M+Na, 100%)+.
4.8.10. 1-O-Caprylyl-2-O-linoleoyl-3-O-(b-D-glucopyr-
anosyl)-rac-glycerol (13b). Yield: 72%. Rf = 0.50
(CH2Cl2/MeOH/10:1, v:v). 1H NMR (400 MHz,
CDCl3): d 0.93 (br t, 6H, J = 6.8 Hz, CH3 term.), 1.25
(br s, 24H, CH2 aliph.), 1.55 (br t, 4H, COCH2CH2),
2.0 (br, 4H, 2· CH2CH@CH), 2.30 (br t, 4H,
J = 7.0 Hz, COCH2), 2.87 (br t, 2H, J = 5.6 Hz,
@CHCH2CH@), 3.28 (m, 1H, H-50), 3.36 (m, 1H, H-
20), 3.56 (m, 1H, H-40), 3.58 (m, 1H, H-30), 3.63, 3.66
4.8.13. 1-O-Caprinyl-2-O-linoleoyl-3-O-(b-D-glucopyr-
ano- syl)-rac-glycerol (14b). Yield: 69%. Rf = 0.50 (CH2
Cl2/MeOH/10:1, v:v). H NMR (400 MHz, CDCl3): d
0.95 (br t, 6H, J = 6.7 Hz, CH3 term.), 1.24 (br s, 28H,
CH2 aliph.), 1.54 (br t, 4H, COCH2CH2), 2.0 (br, 4H,
2· CH2CH@CH), 2.33 (br t, 4H, J = 7.0 Hz, COCH2),
2.88 (br t, 2H, J = 5.6 Hz, @CHCH2CH@), 3.31 (m,
1H, H-50), 3.35 (m, 1H, H-20), 3.56 (m, 1H, H-40), 3.58
1