Molecules 2009, 14
2191
1H, H-3α); 1.76 (s, 3H, H-16); 1.73 (m, 1H, H-6β); 1.63 (bd, J= 9.8 Hz, 1H, H-9); 1.61 (m, 1H, H-
11b), 1.48 (m, 1H, H-11a); 1.31 (dd, J= 13.0 and 4.2 Hz, 1H, H-6α); 1.17 (dd, J= 11.5 and 11.5 Hz,
1H, H-3β); 1.08 (dd, J=12.5 and 2.7 Hz, 1H, H-5); 0.97 (dd, J= 11.5 and 11.5 Hz, 1H, H-1β); 0.91 (s,
3H, H-18); 0.86 (s, 3H, H-19); 0.73 (s, 3H, H-20). 13C-NMR: 48.0 (C-1), 65.6 (C-2), 51.0 (C-3), 35.0
(C-4), 54.8 (C-5), 23.9 (C-6), 38.0 (C-7), 147.7 (C-8), 55.7 (C-9), 40.9 (C-10), 21.9 (C-11), 30.4 (C-
12), 140.3 (C-13), 124.6 (C-14), 59.0 (C-15), 23.4 (C-16), 107.3 (C-17), 33.6 (C-18), 22.6 (C-19), 15.4
(C-20). IR (cm-1): 3,380, 2,940, 1,641, 1,470, 1,445, 1,388, 1,035, 888, 754. M.S. (m/z, %): M+ 306 <
1%, 291 (12.8), 288 (12.8), 273 (57.2), 270 (13.4), 257 (12.9), 255 (50.2), 245 (13.3), 207 (19.9), 205
(18.5), 203 (14.1), 202 (15.1), 199 (12.9), 190 (13.4), 189 (20.5), 188 (13.4), 187 (40.9), 175 (36.1),
173 (17.8), 163 (14.3), 150 (21.5), 149 (18.5), 148 (13.5), 147 (43.6), 145 (25.0), 137 (18.7), 136
(19.7), 135 (100.0), 134 (27.1), 133 (44.0), 131 (21.8), 123 (28.5), 122 (24.1), 121 (68.7), 120 (32.0),
119 (57.5), 117 (16.6), 111 (13.9), 109 (47.8), 108 (22.2), 107 (84.9), 106 (19.4), 105 (59.3), 97 (23.8),
96 (14.5), 95 (67.5), 94 (22.1), 93 (96.2), 92 (14.3), 91 (59.0), 85 (20.4), 84 (23.2), 83 (27.7), 81
(71.2), 80 (16.8), 79 (61.5), 77 (32.6), 71 (25.0), 69 (61.9), 68 (16.9), 67 (47.5), 57 (41.6), 55 (59.0),
53 (24.1).
Fraction II: (0.527 g, 20.4%) viscous oil, mixture of 9-10.
Fraction III: compound 10 (1.43 g, 55.4%) white needles, mp = 104.4-106.2°C (Et2O/MeOH),
[α]D23 = -20.9º (c 1.05, CHCl3); 1H-NMR: 5.38 (bt, J= 6.9 Hz, 1H, H-14); 4.86 (s, 1H, H-17b); 4.54 (s,
1H, H-17a); 4.15 (d, J= 6.9 Hz, 2H, H-15); 3.88 (ddt, J= 12.0, 12.0 and 4.4 Hz, 1H, H-2); 2.40 (ddd,
J= 12.6, 4.4 and 2.5 Hz, 1H, H-7α); 2.16 (ddd, J= 12.0, 9.5 and 4.2 Hz, 1H, H-12b); 2.10 (ddd, J=
11.6, 4.4 and 2.5 Hz, 1H, H-1α); 1.97 (ddd, J= 13.9, 12.6 and 5.1 Hz, 1H, H-7β); 1.84 (dd, J= 9.5 and
6.7 Hz, 1H, H-12a); 1.75 (m, 2H, H-3α and H-6β); 1.67 (s, 3H, H-16); 1.64 (m, 1H, H-11b); 1.63 (bd,
J= 10.3 Hz, 1H, H-9); 1.49 (m, 1H, H-11a); 1.29 (dd, J= 12.6 and 4.2 Hz, 1H, H-6α); 1.15 (dd, J= 12.0
and 12.0 Hz, 1H, H-3β); 1.07 (dd, J=12.6 and 2.5 Hz, 1H, H-5); 0.96 (dd, J= 12.0 and 12.0 Hz, 1H, H-
1β); 0.93 (s, 3H, H-18); 0.84 (s, 3H, H-19); 0.72 (s, 3H, H-20). 13C-NMR: 48.2 (C-1), 65.7 (C-2), 51.1
(C-3), 35.0 (C-4), 54.9 (C-5), 23.9 (C-6), 38.0 (C-7), 147.7 (C-8), 56.2 (C-9), 41.0 (C-10), 22.0 (C-11),
38.3 (C-12), 140.3 (C-13), 123.2 (C-14), 59.4 (C-15), 16.4 (C-16), 107.2 (C-17), 33.7 (C-18), 22.6 (C-
19), 15.4 (C-20). IR (cm-1): 3,339, 2,935, 1646, 1,464, 1,440, 1,388, 1,363, 1,030, 888. M.S. (m/z, %):
M+ 306 1.3%, 291 (22.7), 274 (14.1), 273 (68.2), 270 (11.8), 255 (48.3), 245 (15.1), 203 (13.9), 202
(18.4), 199 (11.9), 190 (14.4), 189 (13.2), 187 (41.2), 175 (33.8), 173 (13.2), 163 (12.4), 161 (27.0),
159 (19.3), 149 (13.3), 148 (13.2), 137 (14.5), 136 (18.3), 135 (100.0), 134 (20.6), 133 (38.5), 131
(19.4), 123 (24.4), 122 (19.3), 121 (62.7), 120 (31.9), 119 (44.1), 109 (42.9), 108 (17.9), 107 (73.9),
106 (13.9), 105 (45.0), 97 (15.8), 95 (50.2), 94 (16.1), 93 (77.6), 92 (11.8), 91 (44.7), 85 (13.4), 83
(20.5), 81 (58.3), 79 (48.9), 77 (23.9), 71 (18.0), 69 (51.2), 68 (14.9), 67 (37.9), 57 (32.7), 55 (42.4),
53 (18.2).
Synthesis of 2β-hydroxy-15-phenyl-(22,25-dihydroxy)-ent-labda-8(17), 13(E)-diene (2) from 9: To a
.
solution of 1,4-hydroquinone (0.086 g, 0.781 mmol) and BF3 THF (0.2 mL, 1.59 mmol) in freshly
distilled 1,4-dioxane (5 mL) was slowly added dropwise with stirring at room temperature and under a
N2 atmosphere, a solution of 9 (0.238 g, 0.777 mmol) in 1,4-dioxane (5 mL). After the addition was
complete, stirring at room temperature and under N2 atmosphere was continued overnight. When the
end of the reaction was verified by TLC, the mixture was poured onto crushed ice (app. 30 g) and the