HETEROCYCLES, Vol. 94, No. 8, 2017
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yellow oil. IR (film) νmax cm-1: 3428, 3070, 2930, 2856, 1606, 1596, 1462, 1428, 1376, 1361, 1345, 1323,
1
1294, 1206, 1151, 1111, 1072, 998, 971, 823; H NMR (500 MHz, CDCl3) δ: 7.69-7.67 (4H, m),
7.42-7.34 (6H, m), 6.37 (2H, d, J = 2.0 Hz), 6.35 (1H, d, J = 2.0 Hz), 5.38-5.29 (2H, m), 3.92-3.81 (2H,
m), 3.78 (6H, s), 2.76 (1H, dd, J = 13.5, 4.0 Hz), 2.55 (1H, dd, J = 13.5, 9.0 Hz), 2.19-2.07 (2H, m),
1.97-1.93 (2H, m), 1.60-1.34 (7H, m), 1.09 (9H, s), 1.04 (3H, d, J = 6.0 Hz); 13C NMR (125 MHz,
CDCl3) δ: 160.9, 140.9, 135.9, 134.8, 134.6, 132.6, 129.4, 127.4, 126.5, 107.3, 98.4, 72.4, 69.6, 55.3,
44.4, 42.8, 36.7, 32.6, 29.5, 27.0, 25.3, 22.9, 19.2 ppm. HRMS-EI: m/z [M]+: Calcd for C35H48OSi;
560.3322, Found: 560.3320.
(7E,10S)-1-(2-Iodo-3,5-dimethoxyphenyl)-10-tert-butyldiphenylsilyloxyundec-7-en-2-ol (18). To a
solution of 9 (49 mg, 87 µmol) in CCl4 (1.7 mL) was added NIS (20 mg, 87 µmol). After the resulting
mixture had been stirred for 1 h, the reaction was quenched with aqueous Na2S2O3. The mixture was
extracted with EtOAc (20 mL x 2) and the organic layer was washed with water, brine, dried over Na2SO4,
filtered, and concentrated. The residue was purified with preparative TLC (toluene : EtOAc = 10:1) to
afford 18 (34 mg, 57%) as a colorless oil. IR (film) νmax cm-1: 3422, 3070, 2929, 2856, 1580, 1455, 1428,
1413, 1325, 1280, 1205, 1163, 1111, 1080, 1010, 971, 823; 1H NMR (500 MHz, CDCl3) δ: 7.69-7.67 (4H,
m), 7.42-7.35 (6H, m), 6.48 (1H, d, J = 2.5 Hz), 6.33 (1H, d, J = 2.5 Hz), 5.37-5.30 (2H, m), 3.94-3.76
(2H, m), 3.86 (3H, s), 3.80 (3H, s), 3.05 (1H, dd, J = 13.8, 4.0 Hz), 2.76 (1H, dd, J = 13.8, 9.0 Hz),
2.19-2.07 (2H, m), 1.98-1.97 (2H, m), 1.68-1.31 (7H, m), 1.09 (9H, s), 1.04 (3H, d, J = 7.5 Hz); 13C NMR
(125 MHz, CDCl3) δ: 160.8, 159.1, 143.6, 135.9, 134.8, 134.6, 132.7, 129.4, 127.4, 126.5, 107.9, 97.1,
82.2, 71.1, 69.6, 56.4, 55.5, 48.8, 42.7, 36.9, 32.6, 29.5, 27.0, 25.2, 22.9, 19.2 ppm. HRMS-EI: m/z [M]+:
Calcd for C35H47IOSi; 686.2289, Found: 686.2284.
(7E,10S)-1-(2-Iodo-3,5-dimethoxyphenyl)-10-tert-butyldiphenylsilyloxyundec-7-en-2-one (8). To a
solution of 18 (86 mg, 0.125 mmol) in CH2Cl2 (2.0 mL) was added Dess-Martin periodinane (68 mg, 0.16
o
mmol) at 0 C. After being stirred for 30 min at room temperature, the reaction was quenched with
o
aqueous NaHCO3/Na2S2O3 (1:1, 10 mL) at 0 C and the mixture had been stirred until the organic layer
was cleared. The mixture was extracted with EtOAc (20 mL x 2) and the organic layer was washed with
water, brine, dried over Na2SO4, filtered, and concentrated. The residue was purified with preparative
TLC (toluene : EtOAc = 10:1) to afford 8 (76 mg, 89%) as a colorless oil. [α]19D −13.7 (c 0.760, CHCl3);
IR (film) νmax cm-1: 3070, 2961, 2930, 2856, 1717, 1581, 1455, 1428, 1375, 1362, 1335, 1306, 1281,
1
1205, 1163, 1111, 971, 823; H NMR (500 MHz, CDCl3) δ: 7.68-7.66 (4H, m), 7.42-7.34 (6H, m), 6.38
(1H, d, J = 2.5 Hz), 6.33 (1H, d, J = 2.5 Hz), 5.34-5.30 (2H, m), 3.88 (2H, s), 3.84 (3H, s), 3.83-3.79 (1H,