Helvetica Chimica Acta – Vol. 91 (2008)
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ether (60 – 908)/AcOEt 18 :1): Fr. 2.1.1 – 2.1.4. Fr. 2.1.4 was further purified by repeated CC (silica gel,
petroleum ether (60 – 908)/AcOEt 15 :1): 2 (10 mg). Fr. 2.2 (petroleum ether (60 – 908)/AcOEt 4 :1;
9.2 g), after further CC (silica gel (200 – 300 mesh; 92 g), petroleum ether (60 – 908)/AcOEt 12 :1) gave
Fr. 2.2.1 and 2.2.2. Fr. 2.2.2, after further CC (silica gel, petroleum ether (60 – 908)/AcOEt 12 :1), gave 1
(48 mg). Fr. 3 (petroleum ether (60 – 908)/acetone 8 :1; 32 g) was separated by CC (silica gel (200 – 300
mesh; 320 g), CHCl3/AcOEt 1:0, 15 :1 and 10 :1): Fr. 3.1 – 3.3. Fr. 3.3 was purified by repeated CC (silica
gel, petroleum ether (60 – 908)/AcOEt/MeOH 10 :2 :0.2): Fr. 3.3.1 – 3.3.3. Fr. 3.3.2 was further purified by
prep. TLC (petroleum ether (60 – 908)/AcOEt/MeOH 10 :3:0.1): 5 (18 mg; Rf 0.4) and 4 (22 mg; Rf
0.35). Fr. 3.3.3 afforded 3 (20 mg; Rf 0.33) by prep. TLC (petroleum ether (60 – 908)/AcOEt/MeOH
10 :5 :0.1).
4-Hydroxybenzoates from Allylic Alcohols. To a soln. of pure compound 1, 2, 3, or 4 (ca. 4 mg) in dry
pyridine and CH2Cl2 under Ar in a dry test tube fitted with a rubber septum, a slight excess of 4-
hydroxybenzoyl chloride was added. After 4 h under magnetic stirring at r.t., the 4-hydroxybenzoate was
isolated by prep. TLC: 1a, 2a, 3a, and 4a.
(2E,6Z,10E,12R)-7-[(Acetyloxy)methyl]-3,11,15-trimethylhexadeca-2,6,10,14-tetraene-1,12-diol (1).
Colorless gum. [a]2D0 ¼ À0.3( c ¼ 2.0, CHCl3). IR (KBr): 3410, 2926, 1737, 1669. 1H- and 13C-NMR:
Tables 1 and 2. HR-ESI-MS: 387.2510 ([M þ Na]þ, C22H36NaO4þ ; calc. 387.2506).
CD of 1a (c ¼ 1.1 g/l, MeOH): 244 (À2316).
(2E,6Z,10E,12R)-7-[(Acetyloxy)methyl]-12-hydroxy-3,11,15-trimethylhexadeca-2,6,10,14-tetraenal
(2). Colorless gum. [a]2D0 ¼ À1.6 (c ¼ 1.6, CHCl3). IR (KBr): 3411, 2965, 1738, 1668. 1H- and 13C-NMR:
Tables 1 and 2. HR-ESI-MS: 385.2351 ([M þ Na]þ, C22H34NaO4þ ; calc. 385.2350).
CD of 2a (c ¼ 1.8 g/l, MeOH): 245 (À4424).
(2E,6Z,12S,13E)-7-[(Acetyloxy)methyl]-3,11,15-trimethylhexadeca-2,6,13-triene-1,12,15-triol (3).
Colorless gum. [a]2D0 ¼ À4.0 (c ¼ 2.0, CHCl3). IR (KBr): 3375, 2929, 1737, 1719, 1667. 1H- and
13C-NMR: Tables 1 and 2. HR-ESI-MS: 400.3065 ([M þ NH4]þ, C22H42NOþ5 ; calc. 400.3057).
CD of 3a (c ¼ 1.5 g/l, MeOH): 243( þ 5093).
(2E,6Z,12R,14S)-7-[(Acetyloxy)methyl]-3,11,15-trimethylhexadeca-2,6,15-triene-1,12,14-triol (4).
Colorless gum. [a]2D0 ¼ þ4.0 (c ¼ 4.0, CHCl3). IR (KBr): 3372, 2926, 1737, 1712, 1657. 1H- and
13C-NMR: Tables 1 and 2. HR-ESI-MS: 383.2798 ([M þ H]þ, C22H39Oþ5 ; calc. 383.2792).
CD of 4a (c ¼ 1.4 g/l, MeOH): 243( þ4092).
rel-(3R,5S)-5-{(1R,5Z,9E)-5-[(Acetyloxy)methyl]-11-hydroxy-1,9-dimethylundeca-5,9-dien-1-yl}te-
trahydro-2,2-dimethylfuran-3-ol (5). Colorless gum. [a]2D0 ¼ À10.0 (c ¼ 1.0, CHCl3). IR (KBr): 3394,
þ
1
2923, 1737, 1663. H- and 13C-NMR: Tables 1 and 2. HR-ESI-MS: 383.2785 ([M þ H]þ, C22H39O5 ; calc.
383.2792).
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Received April 10, 2008