Page 9 of 16
The Journal of Organic Chemistry
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(dt, J = 14.2, 7.1 Hz, 1H), 5.98 (d, J = 14.2 Hz, 1H), 5.63 (m, 1H), 5.27 (dd, J = 8.3 Hz, 15.6 Hz, 1H), 5.11 (d,
J = 9.8 Hz, 1H), 5.06 (dd, J = 9.8 Hz, 9.8 Hz, 1H), 4.98 (dd, J = 7.8, 9.3 Hz, 1H), 4.45 (d, J = 7.8 Hz, 1H),
4.40 (d, J = 7.8 Hz, 1H), 4.29 (m, 1H), 4.20 (dd, J = 4.9, 12.2 Hz, 1H), 4.09 (dd, J = 2.4, 12.2 Hz, 1H), 3.80 (s,
3H), 3.55ꢀ3.43 (m, 5H), 3.38 (s, 3H), 3.15 (s, 3H), 2.51 (m, 1H), 2.37 (m, 1H), 2.14 (m, 1H), 2.09 (s, 3H),
2.09 (s, 3H), 2.05 (s, 3H), 2.03ꢀ1.94 (m, 2H), 1.87 (m, 1H), 1.74 (m, 1H), 1.54 (s, 3H), 0.99 (d, J = 6.3 Hz,
3H); 13C NMR (100 MHz, CDCl3) δ 170.9, 170.0, 169.3, 159.2, 144.9, 133.8, 133.7, 131.6, 131.0, 130.9,
129.3, 113.9, 113.8, 97.7, 86.9, 81.5, 76.1, 75.7, 72.8, 72.0, 71.9, 69.1, 66.4, 62.6, 58.4, 55.9, 55.4, 43.6, 37.6,
35.8, 31.8, 21.1, 21.0, 20.9, 20.8; IR (neat) 2953, 2932, 2868, 1750, 1612, 1513, 1456, 1437, 1373, 1302,
1226, 1173, 1155, 1092, 1038, 970, 904, 823, 599 cmꢀ1 HRMSꢀESI: Exact mass calcd for C37H53INaO12
[M+Na]+: 839.2479; found 839.2462; [α]D24.6 +0.1 (c 1.37, CHCl3).
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(((2R,3R,4S,5R,6R)-2-(((3S,4E,7S,8E,10S,12E)-13-iodo-7-methoxy-1-((4-methoxybenzyl)oxy)-8,10-dime
thyltrideca-4,8,12-trien-3-yl)oxy)-4-methoxy-6-(((triethylsilyl)oxy)methyl)tetrahydro-2H-pyran-3,5-diyl)bis(ox
y))bis(triethylsilane) (12): To a solution of glycoside 11 (33.3 mg, 40.8 µmol) in MeOH (0.5 mL) was added 2
M solution of NaOMe in MeOH (0.5 mL, 1 mmol) and stirred at room temperature for 12 h, then quenched by
addition of DOWEX 50W and filtered. The filtrate was concentrated in vacuo to give triol (26.8 mg) as a
colorless oil. The solution of triol in DMF (0.3 mL) was added imidazole (48.3 mg, 0.71 mmol) and TESCl
(0.05 mL, 0.30 mmol). After stirring at room temperature for 3.5 h, the reaction was quenched by addition of
H2O and extracted with EtOAc (3 × 10 mL). The combined organic layers were washed with brine, dried over
Na2SO4 and concentrated in vacuo. The residue was purified by column chromatography on SiO2
(hexane/EtOAc 15:1 to 10:1) to give TES ether 12 (24.3 mg, 23.5 µmol, 58% in 2 steps) as a colorless oil: 1H
NMR (400 MHz, CDCl3) δ 7.25 (d, J = 8.8 Hz, 2H), 6.86 (d, J = 8.8 Hz, 2H), 6.43 (dt, J = 14.6, 7.8 Hz, 1H),
5.98 (d, J = 14.6 Hz, 1H), 5.58 (dt, J = 14.6, 6.8 Hz, 1H), 5.28 (dd, J = 8.8, 14.6 Hz, 1H), 5.10 (d, J = 9.8 Hz,
1H), 4.41 (s, 2H), 4.29 (dd, J = 7.8, 14.1 Hz, 1H), 4.23 (d, J = 7.3 Hz, 1H), 3.80 (s, 3H), 3.69 (dd, J = 4.9,
11.2 Hz, 1H), 3.52 (s, 3H), 3.52ꢀ3.44 (m, 3H), 3.39 (dd, J = 5.9, 7.3 Hz, 1H), 3.34 (dd, J = 7.8, 7.8 Hz, 1H),
3.15 (s, 3H), 3.06 (m, 1H), 2.93 (dd, J = 8.8, 8.8 Hz, 1H), 2.50 (m, 1H), 2.36 (m, 1H), 2.14 (m, 1H), 2.04ꢀ1.95
(m, 3H), 1.77 (m, 1H), 1.52 (s, 3H), 0.99ꢀ0.93 (m, 27H), 0.67ꢀ0.54 (m, 21H); 13C NMR (100 MHz, CDCl3) δ
159.2, 145.0, 133.8, 133.7, 132.3, 131.1, 130.9, 129.4, 129.3, 113.8, 98.2, 88.5, 86.9, 77.1, 75.8, 74.4, 72.7,
70.9, 67.3, 62.4, 61.8, 55.8, 55.4, 43.6, 37.3, 35.8, 31.9, 20.7, 11.2, 7.1, 7.0, 5.3, 5.2, 4.7 IR (neat) 2952, 2911,
2875, 2359, 1614, 1540, 1513, 1457, 1417, 1375, 1302, 1246, 1095, 1041, 1006, 971, 852, 815, 741 cmꢀ1
HRMSꢀESI: Exact mass calcd for C49H89INaO9Si3 [M+H]+: 1055.4757; found 1055.4751; [α]D26.8 –2.4 (c 1.22,
CHCl3)
(3S,4E,7S,8E,10S,12E)-13-iodo-7-methoxy-3-(((2R,3R,4S,5R,6R)-4-methoxy-3,5-bis((triethylsilyl)oxy)-6
-(((triethylsilyl)oxy)methyl)tetrahydro-2H-pyran-2-yl)oxy)-8,10-dimethyltrideca-4,8,12-trien-1-ol (13): To a
solution of TES ether 12 (26.6 mg, 25.7 µmol) in CH2Cl2 was added 1 M solution of pH 7 phosphate buffer (1
mL) and DDQ (13.6 mg, 59.9 µmol) and stirred at room temperature for 20 min. The reaction mixture was
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