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M. Kudo et al. / Tetrahedron 68 (2012) 4455e4463
purified by column chromatography (ethyl acetate/n-hexane¼1/1)
to give 25 (561 mg, 0.777 mmol, 86%) as a yellow oil.
and stirring was continued for 2.5 h at room temperature. The
solvent was removed in vacuo, and the residue was poured into
water, and extracted with ethyl acetate. The organic layer was
washed with brine, dried over magnesium sulfate, filtered, and
evaporated. The residue was purified by column chromatography
(ethyl acetate/n-hexane¼2/1) to give 7 (69 mg, 0.0458 mmol,
63%) as a colorless oil.
1H NMR (600 MHz, CDCl3)
d
7.72 (d, J¼8.2 Hz, 1H), 7.70 (d,
J¼7.6 Hz, 1H), 7.47 (s, 1H), 7.45 (s, 1H), 7.20 (t, J¼7.9 Hz, 1H),
7.19e7.17 (m, 2H), 7.03 (d, J¼7.4 Hz, 1H), 6.66 (t, J¼7.9 Hz, 1H), 6.47
(d, J¼8.1 Hz, 1H), 6.29 (d, J¼8.4 Hz, 1H), 6.27 (s, 1H), 3.84e3.77 (m,
2H), 3.70e3.48 (m, 12H), 3.37 (s, 3H), 3.33e3.28 (m, 2H), 2.92 (dd,
J¼14.2, 8.8 Hz, 1H), 1.60e1.39 (m, 6H), 1.18 (d, J¼6.2 Hz, 3H), 0.92 (t,
J¼7.4 Hz, 3H), 0.88 (t, J¼7.4 Hz, 3H), 0.86 (t, J¼7.4 Hz, 3H); 13C NMR
1H NMR (600 MHz, CD3OD)
d
7.00 (t, J¼7.6 Hz, 4H), 6.90 (t,
J¼7.4 Hz, 2H), 6.74 (t, J¼7.4 Hz, 1H), 6.73 (t, J¼7.9 Hz, 3H), 6.68 (d,
J¼8.1 Hz, 4H), 6.67 (t, J¼8.3 Hz, 1H), 6.50 (d, J¼7.9 Hz, 1H), 6.43 (d,
J¼8.0 Hz, 1H), 6.40 (d, J¼8.0 Hz, 2H), 6.35e6.31 (m, 4H), 6.26 (s, 1H),
6.25 (d, J¼7.3 Hz, 1H), 6.02 (s, 1H), 6.00 (s, 1H), 5.98 (s, 1H), 5.95 (s,
1H), 3.79e3.76 (m, 1H), 3.72e3.61 (m, 5H), 3.58e3.55 (m, 3H),
3.53e3.49 (m, 1H), 3.46e3.42 (m, 4H), 3.37 (s, 3H), 3.37e3.33 (m,
1H), 3.27e3.09 (m, 16H), 2.85e2.82 (m, 1H), 1.52e1.27 (m, 24H),
1.13 (d, J¼6.2 Hz, 3H), 0.90e0.81 (m, 33H); 13C NMR (150 MHz,
(150 MHz, CDCl3)
d 159.4, 159.0, 148.4, 148.3, 146.3, 145.5, 145.1,
144.5, 132.3, 132.0, 129.4, 129.2, 128.7, 124.0, 123.4, 121.0, 120.5,
119.5, 119.4, 73.8, 72.1, 71.0, 70.7, 67.8, 59.1, 58.4, 53.6, 53.3, 53.2,
21.7, 17.3, 11.5.
4.2.17. Synthesis of 26. 10% Pd on carbon (21 mg) was added to
a solution of 25 (103 mg, 0.142 mmol) in dry methanol (2 mL), and
the reaction mixture was stirred for 4.5 h at room temperature
under a hydrogen atmosphere, then filtered through Celite. The
filtrate was concentrated to give 26 (86 mg, 0.130 mmol, 92%) as
a colorless oil.
CDCl3)
d 161.9, 161.4, 161.4, 161.4, 160.5, 147.2, 146.2, 146.0, 145.9,
145.9, 145.8, 145.6, 145.5, 145.1, 129.7, 129.6, 129.4, 129.4, 129.1,
129.0, 127.6, 126.4, 125.1, 124.8, 124.7, 124.6, 124.5, 124.3, 124.3,
124.2, 124.2, 124.1, 124.1, 124.1, 123.9, 75.1, 73.1, 72.1, 71.6, 69.0, 59.4,
59.2, 54.7, 54.6, 54.6, 54.5, 54.5, 54.4, 54.3, 22.9, 22.8, 22.8, 22.7,
22.7, 22.6, 22.5, 17.6, 11.8, 11.8, 11.7, 11.7, 11.7, 11.7.
1H NMR (600 MHz, CDCl3)
d
6.74 (t, J¼8.0 Hz, 1H), 6.73 (t,
J¼7.9 Hz, 1H), 6.70 (t, J¼7.9 Hz, 1H), 6.52 (d, J¼7.9 Hz, 1H), 6.46 (d,
J¼7.9 Hz, 1H), 6.21 (d, J¼7.9 Hz, 1H), 6.20 (s, 1H), 6.17 (d, J¼7.9 Hz,
1H), 6.07 (s,1H), 6.03 (d, J¼7.4 Hz,1H), 6.02 (d, J¼7.4 Hz,1H), 5.96 (s,
1H), 3.82e3.76 (m, 2H), 3.70e3.62 (m, 5H), 3.55 (br s, 2H), 3.55 (t,
J¼4.7 Hz, 4H), 3.50e3.39 (m, 5H), 3.36 (s, 3H), 3.31 (t, J¼7.8 Hz, 2H),
3.19 (dd, J¼14.0, 7.8 Hz, 1H), 1.72 (br s, 2H), 1.57e1.46 (m, 4H), 1.18
(d, J¼6.2 Hz, 3H), 0.90 (t, J¼7.4 Hz, 3H), 0.84 (t, J¼7.4 Hz, 3H), 0.83 (t,
4.2.20. Synthesis of 28. Phenyl isocyanate (0.024 mL, 0.222 mmol)
was added to a solution of 14 (34 mg, 0.108 mmol) in dry tetra-
hydrofuran (1 mL), and the mixture was stirred for 22 h at 60 ꢁC,
then poured into saturated sodium bicarbonate, and extracted with
ethyl acetate. The organic layer was washed with brine, dried over
magnesium sulfate, filtered, and evaporated. The residue was pu-
rified by column chromatography (silica gel, ethyl acetate/n-
hexane¼1/1) to give 28 (26 mg, 0.0478 mmol, 38%) as a colorless
oil.
J¼7.4 Hz, 3H); 13C NMR (150 MHz, CDCl3)
d 160.4, 160.1, 146.9, 146.8,
146.4, 145.3, 144.9, 144.7, 129.1, 128.9, 127.6, 124.7, 123.7, 123.4,
116.8, 116.5, 113.6, 113.5, 112.0, 111.7, 74.2, 72.0, 71.1, 70.6, 68.0, 59.1,
57.8, 53.4, 53.3, 21.7, 21.7, 21.7, 17.8, 11.6, 11.5, 11.5.
1H NMR (600 MHz, CDCl3)
d
7.74 (br s, 1H), 7.50 (t, J¼8.0 Hz,1H),
4.2.18. Synthesis of 27. A solution of 15 (131 mg, 0.421 mmol) in
1,2-dichloroethane (1.0 mL) was added to a solution of triphosgene
(43 mg, 0.146 mmol) in 1,2-dichloroethane (0.5 mL), and the re-
action mixture was stirred at room temperature for 1.5 h. After
concentration, the residual isocyanate was dissolved in dry tetra-
hydrofuran (0.5 mL). A solution of 26 (94 mg, 0.142 mmol) in dry
tetrahydrofuran (1.0 mL) was added to the isocyanate solution, and
this mixture was stirred for 2.5 h at room temperature, then poured
into saturated sodium bicarbonate, and extracted with ethyl ace-
tate. The organic layer was dried over magnesium sulfate, filtered,
and evaporated. The residue was purified by column chromatog-
raphy (ethyl acetate/n-hexane¼3/1) to give 27 (97 mg,
0.0727 mmol, 51%) as a white solid.
7.39e7.34 (m, 6H), 7.27e7.21 (m, 5H), 7.01 (t, J¼7.4 Hz, 1H), 6.98 (t,
J¼7.5 Hz, 1H), 6.40 (br s, 1H), 3.90e3.81 (m, 3H), 3.76e3.72 (m,
3H), 3.60 (t, J¼4.6 Hz, 2H), 3.57e3.50 (m, 3H), 3.41 (t, J¼4.6 Hz,
2H), 3.25 (s, 3H), 1.62 (sextet, J¼7.5 Hz, 2H), 1.18 (d, J¼6.1 Hz, 3H),
0.92 (t, J¼7.4 Hz, 3H); 13C NMR (150 MHz, CDCl3)
d 155.7, 154.2,
145.2, 142.9, 139.3, 139.1, 131.1, 129.0, 128.8, 127.7, 126.4, 126.1,
123.0, 119.7, 119.3, 75.8, 71.9, 70.6, 70.5, 68.6, 59.0, 56.4, 51.3, 21.9,
17.2, 11.4.
4.2.21. Synthesis of 8. Sodium hydride (7 mg, 0.175 mmol) was
washed with n-hexane, and suspended in dry dimethylformamide
(0.3 mL). A solution of 28 (22 mg, 0.040 mmol) in dry dime-
thylformamide (0.3 mL) was added to the suspension at 0 ꢁC. The
reaction mixture was stirred for 1 h at room temperature, then 1-
iodopropane (0.04 mL, 0.412 mmol) was added, and stirring was
continued for 4.5 h at room temperature. The solvent was re-
moved in vacuo, and the residue was poured into water, and
extracted with ethyl acetate. The organic layer was washed with
brine, dried over magnesium sulfate, filtered, and evaporated. The
residue was purified by preparative thin-layer chromatography
(ethyl acetate/n-hexane¼1/1) to give 8 (19 mg, 0.029 mmol, 74%)
as a colorless oil.
1H NMR (600 MHz, CD3OD)
d 7.08e7.04 (m, 6H), 6.99e6.87 (m,
13H), 6.80 (d, J¼7.6 Hz, 4H), 6.62 (d, J¼7.9 Hz, 1H), 6.56 (d,
J¼7.9 Hz, 1H), 6.41e6.39 (m, 2H), 6.36 (d, J¼7.6 Hz, 1H), 6.28 (d,
J¼7.9 Hz, 1H), 6.24 (s, 1H), 3.82 (t, J¼8.8 Hz, 1H), 3.78e3.70 (m,
5H), 3.64e3.42 (m, 16H), 3.32 (s, 3H), 3.30 (t, J¼7.9 Hz, 2H),
2.97e2.95 (m, 1H), 1.61e1.48 (m, 14H), 1.13 (d, J¼6.3 Hz, 3H), 0.97
(t, J¼7.4 Hz, 3H), 0.91e0.85 (m, 18H); 13C NMR (150 MHz, CD3OD)
d
162.5, 161.9, 161.8, 154.2, 147.6, 145.9, 145.9, 145.8, 145.5, 145.2,
141.0, 141.0, 141.0, 140.8, 130.0, 129.9, 129.7, 129.6, 129.3, 128.1,
128.1, 126.3, 126.3, 126.0, 125.1, 124.8, 122.1, 121.9, 121.8, 121.1,
118.6, 118.4, 118.3, 118.1, 116.7, 116.6, 116.4, 75.7, 72.8, 72.5, 71.7,
68.8, 59.1, 59.1, 54.6, 54.5, 54.5, 54.4, 54.4, 54.3, 22.8, 22.6, 22.6,
22.5, 17.6, 12.0, 11.8, 11.8, 11.7.
1H NMR (600 MHz, CDCl3)
d
6.95 (t, J¼7.5 Hz, 2H), 6.94 (t,
J¼7.6 Hz, 2H), 6.87 (t, J¼7.3 Hz, 1H), 6.85 (t, J¼7.3 Hz, 1H), 6.66 (d,
J¼7.3 Hz, 2H), 6.64 (t, J¼8.0 Hz, 1H), 6.61 (d, J¼7.4 Hz, 2H), 6.43 (d,
J¼7.9 Hz, 1H), 6.35 (d, J¼7.9 Hz, 1H), 6.08 (s, 1H), 3.81e3.65 (m, 6H),
3.63e3.59 (m, 1H), 3.57 (t, J¼4.6 Hz, 2H), 3.52e3.42 (m, 5H), 3.39 (s,
3H), 3.27 (t, J¼7.6 Hz, 2H), 3.04 (dd, J¼14.1, 8.0 Hz, 1H), 1.58e1.43
(m, 6H), 1.17 (d, J¼6.2 Hz, 3H), 0.90 (t, J¼7.4 Hz, 3H), 0.84 (t,
J¼7.3 Hz, 3H), 0.83 (t, J¼7.4 Hz, 3H); 13C NMR (150 MHz, CDCl3)
4.2.19. Synthesis of 7. Sodium hydride (19 mg, 0.788 mmol) was
washed with n-hexane, and suspended in dry dimethylforma-
mide (0.3 mL). A solution of 27 (97 mg, 0.073 mmol) in dry
dimethylformamide (0.6 mL) was added to the suspension at
d
160.5, 160.0, 146.4, 144.7, 144.4, 144.0, 128.5, 128.3, 127.9, 126.8,
0
ꢁC. The reaction mixture was stirred for 30 min at room tem-
126.7, 125.0, 124.9, 124.4, 123.5, 123.2, 74.2, 72.2, 71.1, 70.8, 68.1,
59.2, 57.9, 53.5, 53.4, 21.7, 21.7, 21.7, 17.8, 11.5, 11.5.
perature, then 1-iodopropane (0.08 mL, 0.82 mmol) was added,