5020 Journal of Medicinal Chemistry, 2007, Vol. 50, No. 20
Cisneros et al.
(m, 6H, H7, H10, H13); 3.37-3.59 (m, 2H, 2H tetrahydropyran);
3.96-4.13 (m, 3H, H1′′, 1H tetrahydropyran); 5.23-5.37 (m, 8H,
vinylic-H). 13C NMR (CDCl3, δ): 14.0; 22.6; 23.0; 24.8; 25.6 (3C);
25.7; 26.6; 27.2; 27.9; 29.3; 31.5; 33.6; 67.3; 68.4; 75.5; 127.5;
127.9; 128.2; 128.6; 128.8 (2C); 129.0; 130.5; 173.5. Chromatog-
raphy in hexane/ethyl acetate (9:1).
Tetrahydro-2H-pyran-4-yl (5Z,8Z,11Z,14Z)-Icosa-5,8,11,14-
tetraenoate (6). Yield: 23%. Rf ) 0.51 in chloroform. IR (CHCl3,
cm-1): 1362, 1456, 1558, 1653, 1684, 1716, 2933, 3018. 1H NMR
(CDCl3, δ): 0.89 (t, J ) 6.6 Hz, 3H, H20); 1.22-1.39 (m, 6H, H17,
H18, H19); 1.57-1.78 (m, 4H, H3, 2H tetrahydropyran); 1.85-1.95
(m, 2H, 2H tetrahydropyran); 2.00-2.17 (m, 4H, H4, H16); 2.32 (t,
J ) 7.5 Hz, 2H, H2); 2.78-2.86 (m, 6H, H7, H10, H13); 3.47-3.59
(m, 2H, 2H tetrahydropyran); 3.86-3.96 (m, 2H, 2H tetrahydro-
pyran); 4.95 (sept, J ) 4.3 Hz, 1H, C-H-O tetrahydropyran);
5.27-5.47 (m, 8H, vinylic-H). 13C NMR (CDCl3, δ): 14.2; 22.7;
25.0; 25.8 (3C); 26.7; 27.4; 29.5; 31.7; 32.0 (2C); 34.1; 65.5; 69.1;
76.5; 127.7; 128.0; 128.3; 128.4; 128.7; 129.0 (2C); 130.7; 173.4.
Chromatography in hexane/ethyl acetate (9:1).
6.7 Hz, 3H, H18); 1.15-1.24 (m, 20H, H4-7, H12-17); 1.53-1.57
(m, 2H, H3); 1.89-1.96 (m, 4H, H8, H11); 2.28 (t, J ) 7.3 Hz, 2H,
H2); 2.58 (dd, J ) 4.9; 2.6 Hz, 1H, 1H oxirane); 2.78 (t, J ) 4.9
Hz, 1H, 1H oxirane); 3.12-3.15 (m, 1H, 1H oxirane); 3.84 (dd, J
) 12.3; 6.3 Hz, 1H, 1H1′′); 4.35 (dd, J ) 12.3; 3.0 Hz, 1H, 1H1′′);
5.25-5.31 (m, 2H, vinylic-H). 13C NMR (CDCl3, δ): 14.1; 22.6;
24.8; 27.1; 27.2; 29.1 (3C); 29.3 (2C); 29.5; 29.6; 29.7; 31.9; 34.0;
44.6; 49.3; 64.7; 129.7; 130.0; 173.1. Chromatography in hexane/
ethyl acetate (9:1).
(()-Oxiran-2-ylmethyl (9Z)-Hexadec-9-enoate (12). Yield:
25%. Rf ) 0.50 in chloroform. IR (CHCl3, cm-1): 1551, 1743,
1
2856, 2928. H NMR (CDCl3, δ): 0.88 (t, J ) 6.8 Hz, 3H, H16);
1.28-1.30 (m, 16H, H4-7, H12-15); 1.59-1.67 (m, 2H, H3); 1.99-
2.02 (m, 4H, H8, H11); 2.35 (t, J ) 7.1 Hz, 2H, H2); 2.63 (dd, J )
4.9; 2.4 Hz, 1H, 1H oxirane); 2.84 (dd, J ) 4.9; 4.2 Hz, 1H, 1H
oxirane); 3.16-3.24 (m, 1H, 1H oxirane); 3.90 (dd, J ) 12.2; 6.3
Hz, 1H, 1H1′′); 4.41 (dd, J ) 12.3; 3.2 Hz, 1H, 1H1′′); 5.26-5.37
(m, 2H, vinylic-H). 13C NMR (CDCl3, δ): 14.0; 22.6; 24.8; 27.1;
27.2; 28.9; 29.0 (2C); 29.1; 29.6; 29.7; 31.7; 34.0; 44.6; 49.3; 64.7;
129.7; 130.0; 173.5. Chromatography in hexane/chloroform (2:8).
2-(5,5-Dimethyl-1,3-dioxan-2-yl)ethyl (5Z,8Z,11Z,14Z)-Icosa-
5,8,11,14-tetraenoate (7). Yield: 41%. Rf ) 0.40 in chloroform.
IR (CHCl3, cm-1): 1094, 1456, 1472, 1732. 1H NMR (CDCl3, δ):
0.72 (s, 3H, CH3); 0.89 (t, J ) 6.8 Hz, 3H, H20); 1.18 (s, 3H, CH3);
1.23-1.43 (m, 6H, H17, H18, H19); 1.70 (qt, J ) 7.3 Hz, 2H, H3);
1.96 (q, 2H, J ) 6.6 Hz, H2′′); 2.04-2.17 (m, 4H, H4, H16); 2.31
(t, J ) 7.3 Hz, 2H, H2); 2.78-2.86 (m, 6H, H7, H10, H13); 3.41 (d,
J ) 10.5 Hz, 2H, 2H dioxane); 3.60 (d, J ) 11.0 Hz, 2H, 2H
dioxane); 4.20 (t, J ) 6.6 Hz, 2H, H1′′); 4.53 (t, J ) 5.1 Hz, 1H,
1H dioxane); 5.26-5.46 (m, 8H, vinylic-H). 13C NMR (CDCl3,
δ): 14.0; 21.8; 22.6; 22.9; 24.8; 25.6 (3C); 26.6; 27.2; 29.3; 30.1;
31.5; 33.7; 34.1; 60.0; 77.2 (2C); 99.4; 127.5; 127.9; 128.1; 128.2;
128.6; 128.8; 129.0; 130.5; 173.4. Chromatography in chloroform.
1,3-Benzodioxol-5-ylmethyl (5Z,8Z,11Z,14Z)-Icosa-5,8,11,14-
tetraenoate (8). Yield: 74%. Rf ) 0.35 in hexane/dichloromethane
(1:1). IR (CHCl3, cm-1): 1447, 1491, 1504, 1728, 2930, 2959,
(()-Tetrahydro-2H-pyran-2-ylmethyl (9Z,12Z,15Z)-Octadeca-
9,12,15-trienoate (13). Yield: 55%. Rf ) 0.20 in hexane/chloroform
(2:8). IR (CHCl3, cm-1): 1558, 1732, 2856, 2935, 3016. 1H NMR
(CDCl3, δ): 0.90 (t, J ) 7.5 Hz, 3H, H18); 1.23-1.42 (m, 10H,
H4-7, 2H tetrahydropyran); 1.46-1.67 (m, 5H, H3, 3H tetrahydro-
pyran); 1.80-1.91 (m, 1H, 1H tetrahydropyran); 1.94-2.08 (m,
4H, H8, H17); 2.28 (t, J ) 7.5 Hz, 2H, H2); 2.71-2.76 (m, 4H, H11,
H14); 3.31-3.49 (m, 2H, 2H tetrahydropyran); 3.88-4.06 (m, 3H,
H1′′, 1H tetrahydropyran); 5.18-5.39 (m, 6H, vinylic-H). 13C NMR
(CDCl3, δ): 14.3; 20.6; 23.0; 25.0; 25.5; 25.6; 25.8; 27.2; 27.9;
29.1 (2C); 29.2; 29.6; 34.2; 67.3; 68.4; 75.5; 127.1; 127.7; 128.3
(2C); 130.3; 132.0; 173.9. Chromatography in hexane/chloroform
(2:8).
(()-Tetrahydro-2H-pyran-2-ylmethyl (9Z,12Z)-Octadeca-
9,12-dienoate (14). Yield: 44%. Rf ) 0.12 in hexane/chloroform
(1:1). IR (CHCl3, cm-1): 1558, 1653, 1734, 2856, 2930, 3018. 1H
NMR (CDCl3, δ): 0.82 (t, J ) 6.7 Hz, 3H, H18); 1.09-1.32 (m,
16H, H4-7, H15-17, 2H tetrahydropyran); 1.40-1.61 (m, 5H, H3,
3H tetrahydropyran); 1.77-1.82 (m, 1H, 1H tetrahydropyran);
1.93-1.99 (m, 4H, H8, H14); 2.28 (t, J ) 7.3 Hz, 2H, H2); 2.70 (t,
J ) 5.7 Hz, 2H, H11); 3.31-3.49 (m, 2H, 2H tetrahydropyran);
3.88-4.06 (m, 3H, H1′′, 1H tetrahydropyran); 5.19-5.31 (m, 4H,
vinylic-H). 13C NMR (CDCl3, δ): 14.0; 22.5; 23.0; 24.9; 25.6; 25.7;
27.2 (2C); 27.8; 29.1 (2C); 29.2; 29.3; 29.6; 31.5; 34.2; 67.2; 68.4;
75.5; 127.9; 128.0; 130.0; 130.2; 173.8. Chromatography in hexane/
chloroform (1:1).
1
3016. H NMR (CDCl3, δ): 0.81 (t, J ) 6.6 Hz, 3H, H20); 1.18-
1.32 (m, 6H, H17, H18, H19); 1.64 (qt, J ) 7.4 Hz, 2H, H3); 1.93-
2.08 (m, 4H, H4, H16); 2.28 (t, J ) 7.5 Hz, 2H, H2); 2.68-2.76 (m,
6H, H7, H10, H13); 4.94 (s, 2H, H1′′); 5.20-5.37 (m, 8H, vinylic-
H); 5.89 (s, 2H, O-CH2-O); 6.68-6.78 (m, 3H, Ar). 13C NMR
(CDCl3, δ): 14.5; 23.0; 25.2 (2C); 26.0; 27.0; 27.6; 29.4; 29.7;
31.9; 34.1; 66.5; 101.6; 108.6; 109.4; 122.7; 127.9; 128.3; 128.5;
128.6; 129.0; 129.3 (2C); 130.2; 130.9; 148.0; 148.2; 173.8.
Chromatography in hexane/dichloromethane (1:1).
(()-Oxiran-2-ylmethyl (9Z,12Z,15Z)-Octadeca-9,12,15-trienoate
(9). Yield: 19%. Rf ) 0.67 in chloroform. IR (CHCl3, cm-1): 1653,
1
1732, 2858, 2933, 3020. H NMR (CDCl3, δ): 0.98 (t, J ) 7.5
(()-Tetrahydro-2H-pyran-2-ylmethyl (9Z)-Octadec-9-enoate
(15). Yield: 91%. Rf ) 0.13 in hexane/chloroform (1:1). IR (CHCl3,
Hz, 3H, H18); 1.25-1.31 (m, 8H, H4, H5, H6, H7); 1.60-1.67 (m,
2H, H3); 2.01-2.21 (m, 4H, H8, H17); 2.36 (t, J ) 7.6 Hz, 2H,
H2); 2.58 (dd, J ) 4.9; 2.6 Hz, 1H, 1H oxirane); 2.78-2.87 (m,
5H, H11, H14, 1H oxirane); 3.17-3.26 (m, 1H, 1H oxirane); 3.91
(dd, J ) 12.2; 5.8 Hz, 1H, 1H1′′); 4.42 (dd, J ) 12.2; 2.9 Hz, 1H,
1H1′′); 5.25-5.46 (m, 6H, vinylic-H). 13C NMR (CDCl3, δ): 14.3;
20.6; 24.9; 25.5; 25.6 (2C); 27.2; 29.1; 29.2; 29.6; 34.1; 44.7; 49.4;
64.8; 127.1; 127.8; 128.3 (2C); 130.3; 132.0; 183.0. Chromatog-
raphy in hexane/dichloromethane (2:8).
1
cm-1): 1558, 1734, 2928, 3018. H NMR (CDCl3, δ): 0.81 (t, J
) 6.7 Hz, 3H, H18); 1.18-1.24 (m, 22H, H4-7, H12-17, 2H
tetrahydropyran); 1.39-1.55 (m, 5H, H3, 3H tetrahydropyran);
1.77-1.82 (m, 1H, 1H tetrahydropyran); 1.92-1.98 (m, 4H, H8,
H11); 2.28 (t, J ) 7.3 Hz, 2H, H2); 3.31-3.49 (m, 2H, 2H
tetrahydropyran); 3.88-4.06 (m, 3H, H1′′, 1H tetrahydropyran);
5.20-5.36 (m, 2H, vinylic-H). 13C NMR (CDCl3, δ): 14.2; 22.8;
23.1; 25.0; 25.9; 27.3; 27.4; 28.0; 29.2 (2C); 29.3 (2C); 29.4; 29.7;
29.8; 29.9; 32.0; 34.3; 67.4; 68.5; 75.6; 129.9; 130.1; 174.0.
Chromatography in hexane/chloroform (1:1).
(()-Oxiran-2-ylmethyl (9Z,12Z)-Octadeca-9,12-dienoate (10).
Yield: 36%. Rf ) 0.30 in dichloromethane. IR (CHCl3, cm-1):
1
1379, 1437, 1460, 1732, 2858, 2932. H NMR (CDCl3, δ): 0.88
(t, J ) 6.5 Hz, 3H, H18); 1.18-1.35 (m, 14H, H4-7, H15-17); 1.60-
1.67 (m, 2H, H3); 2.00-2.06 (m, 4H, H8, H14); 2.35 (t, J ) 7.3 Hz,
2H, H2); 2.65 (dd, J ) 4.9; 2.6 Hz, 1H, 1H oxirane); 2.77 (t, J )
5.7 Hz, 2H, H11); 2.82-2.87 (m, 1H, 1H oxirane); 3.17-3.25 (m,
1H, 1H oxirane); 3.90 (dd, J ) 12.3; 6.3 Hz, 1H, 1H1′′); 4.41 (dd,
J ) 12.3; 3.0 Hz, 1H, 1H1′′); 5.25-5.45 (m, 4H, vinylic-H). 13C
NMR (CDCl3, δ): 14.2; 22.7; 24.9; 25.7; 27.3 (2C); 29.2 (3C);
29.4; 29.7; 31.6; 34.2; 44.7; 49.5; 64.8; 128.0; 128.1; 130.1; 130.3;
173.6. Chromatography in hexane/dichloromethane (2:8).
(()-Tetrahydro-2H-pyran-2-ylmethyl (9Z)-Hexadec-9-enoate
(16). Yield: 69%. Rf ) 0.10 in hexane/chloroform (1:1). IR (CHCl3,
1
cm-1): 1558, 1734, 2930, 3018. H NMR (CDCl3, δ): 0.81 (t, J
) 6.7 Hz, 3H, H
16); 1.18-1.34 (m, 18H, H4-7, H12-15, 2H
tetrahydropyran); 1.40-1.58 (m, 5H, H3, 3H tetrahydropyran);
1.77-1.82 (m, 1H, 1H tetrahydropyran); 1.85-2.03 (m, 4H, H8,
H11); 2.28 (t, J ) 7.3 Hz, 2H, H2); 3.31-3.52 (m, 2H, 2H
tetrahydropyran); 3.88-4.06 (m, 3H, H1′′, 1H tetrahydropyran);
5.19-5.35 (m, 2H, vinylic-H). 13C NMR (CDCl3, δ): 14.1; 22.6;
23.0; 25.0; 25.8; 27.2 (2C); 27.9; 29.0; 29.1 (2C); 29.2; 29.7; 29.8;
31.8; 34.2; 67.3; 68.4; 75.5; 129.8; 130.0; 173.9. Chromatography
in hexane/chloroform (1:1).
(()-Oxiran-2-ylmethyl (9Z)-Octadec-9-enoate (11). Yield:
33%. Rf ) 0.51 in chloroform. IR (CHCl3, cm-1): 1456, 1558,
1653, 1734, 2856, 2928, 3018. 1H NMR (CDCl3, δ): 0.81 (t, J )