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HETEROCYCLES, Vol. 77, No. 2, 2009
7.5 Hz), 1.78 (1H, m), 1.68-1.42 (7H, m), 1.40-1.21 (3H, m), 0.89 (3H, t, J = 7.4 Hz), 0.86 (9H, s), 0.03
(3H, s), 0.03 (3H, s); 13C-NMR (100 MHz, CDCl3) δ : 170.3, 139.5, 131.1, 125.9, 112.6, 88.7, 79.9, 75.1,
70.0, 62.7, 60.3, 56.0, 44.9, 42.4, 36.3, 32.8, 27.2, 26.9, 25.9, 22.8, 21.7, 21.1, 18.1, 9.3, -3.8, -4.5;
ESIMS m/z: 513 (M++Na, 100); HRESIMS m/z: 513.3025 (Calcd for C28H46O5NaSi: M++Na, 513.3012).
To a solution of the above diols (72.9 mg, 192 μmol) in CH2ClCH2Cl (9.60 mL), were added MS 4A (96
mg), NMO (110 mg, 960 μmol) and TPAP (6.7 mg, 19.2 μmol). After stirring at rt for 30 min, the
reaction mixture was diluted with Et2O, filtered through silica gel and concentrated under reduced
pressure. The residue was purified by silica gel column chromatography (hexane : AcOEt = 1 : 1) to give
1
a mixture of lactones (48.4 mg, 67% yield) as colorless oil: IR (neat) cm-1: 2930, 2880, 1736; H-NMR
(400 MHz, CDCl3) δ : 5.97 (1H, dd, J = 16.0, 6.8 Hz), 5.71 (2H, m), 5.63 (1H, dt, J = 15.3, 5.0 Hz), 5.18
(1H, m), 4.24 (1H, dt, J = 11.7, 2.5 Hz), 3.46 (1H, m), 3.40 (1H, m), 3.08 (2H, d, J = 4.9 Hz), 2.76 (1H, dt,
J = 0.9, 9.1 Hz), 2.60 (1H, m), 2.42 (1H, ddd, J = 17.8, 9.2, 7.4 Hz), 2.12 (1H, dd, J = 13.4, 7.4 Hz), 2.05
13
(3H, s), 1.93-1.72 (4H, m), 1.64 (3H, m), 1.52 (1H, m), 0.89 (3H, t, J = 7.4 Hz); C-NMR (100 MHz,
CDCl3) δ : 171.7, 170.2, 139.8, 129.9, 127.3, 112.5, 88.2, 80.2, 78.3, 75.0, 59.9, 55.6, 44.4, 43.0, 29.4,
27.3, 27.2, 27.1, 22.6, 21.1, 18.7, 9.3; ESIMS m/z: 395 (M++Na, 82), 327 (100); HRESIMS m/z: 395.1834
(Calcd for C22H28O4Na: M++Na, 395.1834).
A solution of the above lactones (28.2 mg, 75.3 μmol) in EtOH (1.50 mL) in the presence of 5% Pd on
BaSO4 (11.3 mg) and quinoline (14.1 μL) was stirred at rt for 16 h under a hydrogen atmosphere. The
reaction mixture was diluted with Et2O and filtered through silica gel and the filtrate was concentrated
under reduced pressure. The residue was purified by silica gel column chromatography (hexane : acetone
= 3 : 1) to give mixture of trienes. Trienens were separation by HPLC (CHIRALPAK AS-H, 0.46 cm x 25
cm, hexane : isopropanol = 82 : 18, flow rate: 2.0 mL/min) to give triene 23 (tR = 20.2 min, 5.4 mg, 19%
20
yield) and triene 24 (tR = 28.2 min, 5.0 mg, 17% yield); 23: [α]D -179.6˚ (c 0.52, CHCl3); IR (neat)
cm-1: 2924, 1734; 1H-NMR (400 MHz, CDCl3) δ : 6.49 (1H, dd, J = 15.2, 11.0 Hz), 6.01 (1H, t, J = 11.0
Hz), 5.63 (1H, dt, J = 15.4, 6.2 Hz), 5.60 (1H, dd, J = 15.5, 7.0 Hz), 5.48 (2H, m), 5.22 (1H, q, J = 6.8
Hz), 4.24 (1H, dt, J = 11.7, 2.6 Hz), 3.46 (1H, br s), 3.40 (1H, dd, J = 2.6, 1.4 Hz), 2.94 (2H, dd, J = 6.9,
6.8 Hz), 2.71 (1H, t, J = 8.9 Hz), 2.61 (1H, m), 2.42 (1H, ddd, J = 17.7, 9.2, 7.4 Hz), 2.12 (1H, dd, J =
13.5, 7.5 Hz), 2.06 (3H, s), 1.95-1.49 (7H, m), 0.90 (3H, t, J = 7.4 Hz); 13C-NMR (100 MHz, CDCl3) δ :
171.8, 170.4, 131.6, 131.2, 130.3, 129.0, 128.4, 127.7, 78.5, 75.9, 60.1, 55.6, 44.7, 43.2, 30.9, 29.5, 27.5,
27.5, 27.2, 21.3, 18.8, 9.5; ESIMS m/z: 397 (M++Na, 88), 315 (100); HRESIMS m/z: 397.1966 (Calcd for
24
C22H30O5Na: M++Na, 397.1991). 24: [α]D +165.2˚ (c 0.50, CHCl3); IR (neat) cm-1: 2925, 1733;
1H-NMR (400 MHz, CDCl3) δ : 6.49 (1H, dd, J = 15.3, 11.1 Hz), 6.01 (1H, t, J = 10.8 Hz), 5.64 (1H, dt, J
= 15.4, 6.1 Hz), 5.60 (1H, dd, J = 14.8, 7.4 Hz), 5.48 (2H, m), 5.21 (1H, q, J = 6.8 Hz), 4.24 (1H, dt, J =
11.7, 2.6 Hz), 3.46 (1H, br s), 3.40 (1H, dd, J = 2.6, 1.4 Hz), 2.94 (2H, dd, J = 7.5, 6.2 Hz), 2.72 (1H, t, J