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T. Kumazawa et al. / Carbohydrate Research 334 (2001) 183–193
benzylic CH2), 4.99 (d, 1 H, J1%%,2%%=9.6 Hz,
H-1%%), 5.19 (s, 2 H, benzylic CH2), 5.21 (s, 2
H, benzylic CH2), 6.47–7.71 (m, 35 H, ArH
and H-3), 13.07 (br. s, 1 H, ArOH); FABMS
(positive-ion mode, NBA matrix): m/z 1004
[M+H]+. Anal. Calcd for C64H58O11: C,
76.63; H, 5.83. Found: C, 76.56; H, 5.80.
2-(3,4-Bis-benzyloxyphenyl)-8-C-(2,3,4,6-
1136, 1117, 1103, 1066, 1028, 1005, 980, 908,
1
845, 806, 735, 696 cm−1; H NMR (DMSO-d6
at 140 °C): l 3.52 (dt, 1 H, J5%%,6%% 3.5, J4%%,5%% 9.5
Hz, H-5%%), 3.61 (t, 1 H, J3%%,4%%=J4%%,5%% 9.5 Hz,
H-4%%), 3.68–3.71 (m, 3 H, H-3%%,6%%a,6%%b), 3.84
(s, 3 H, ꢀOMe), 4.20 (d, 1 H, Jgem 11.4 Hz,
benzylic CH2), 4.31 (br. t, 1 H, J 9.3 Hz,
H-2%%), 4.46 (d, 1 H, Jgem 12.3 Hz, benzylic
CH2), 4.49 (d, 1 H, Jgem 11.4 Hz, benzylic
CH2), 4.55 (d, 1 H, Jgem 12.3 Hz, benzylic
CH2), 4.63 (d, 1 H, J 11.4 Hz, benzylic CH2),
4.78 (d, 1 H, Jgem 11.4 Hz, benzylic CH2), 4.80
(d, 1 H, Jgem 11.8 Hz, benzylic CH2), 4.84 (d,
1 H, Jgem 11.8 Hz, benzylic CH2), 4.85 (d, 1 H,
J1%%,2%%=9.8 Hz, H-1%%), 5.04 (s, 2 H, benzylic
CH2), 5.17 (s, 2 H, benzylic CH2), 5.27 (s, 2 H,
benzylic CH2), 6.37 (s, 1 H, ArH), 6.89-7.46
(m, 38 H, ArH), 7.54 (d, 1 H, Ja,b 15.6 Hz,
trans-vinyl), 7.59 (d, 1 H, Ja,b 15.6 Hz, trans-
vinyl), 13.48 (br. s, 1 H, ArOH); FABMS
(positive-ion mode, NBA matrix): m/z 1096
[M+H]+. Anal. Calcd for C71H66O11: C,
77.86; H, 6.07. Found: C, 77.73; H, 6.14.
2-(3,4-Bis-benzyloxyphenyl)-8-C-(2,3,4,6-
tetra-O-benzyl-i- -glucopyranosyl)-5,7-di-
D
methoxy-4 H-1-benzopyran-4-one (16).—The
reaction using a compound 15 (804 mg, 0.80
mmol), Me2SO4 (152 mL, 1.60 mmol, 2.0
equiv), K2CO3 (443 mg, 3.21 mmol, 4.0 equiv)
and acetone (10 mL), and the post-treatment
and isolation were carried out in the same
manner as described above for 10. Compound
16 was obtained (782 mg, 96%) as a colorless
amorphous powder: mp 59–60 °C; [h]2D5 −9°
(c 1.0, CHCl3); Rf 0.26 (EtOAc); IR (KBr): w
3087, 3062, 3030, 3006, 2933, 2906, 2864,
1645, 1599, 1576, 1512, 1496, 1454, 1435,
1383, 1336, 1323, 1265, 1209, 1144, 1109,
1066, 1045, 1028, 957, 912, 845, 810, 735, 696
1
cm−1; H NMR (DMSO-d6 at 140 °C): l 3.61
(dt, 1 H, J5%%,6%% 3.2, J4%%,5%% 9.3 Hz, H-5%%), 3.71 (d,
2 H, J5%%,6%% 3.2 Hz, H-6%%a,6%%b), 3.73 (t, 1 H,
J3%%,4%%=J4%%,5%% 9.3 Hz, H-4%%), 3.78 (dd, 1 H, J2%%,3%%
8.5, J3%%,4%% 9.3 Hz, H-3%%), 3.906 (s, 3 H, ꢀOMe),
3.909 (s, 3 H, ꢀOMe), 4.06 (d, 1 H, Jgem 11.0
Hz, benzylic CH2), 4.24 (br. t, 1 H, J 9.2 Hz,
H-2%%), 4.42 (br. m, 3 H, benzylic CH2), 4.61
(d, 1 H, Jgem 11.5 Hz, benzylic CH2), 4.75 (d,
1 H, Jgem 11.5 Hz, benzylic CH2), 4.77 (d, 1 H,
Jgem 11.7 Hz, benzylic CH2), 4.81 (d, 1 H, Jgem
11.7 Hz, benzylic CH2), 5.05 (d, 1 H, J1%%,2%% 9.8
Hz, H-1%%), 5.16 (s, 2 H, benzylic CH2), 5.19 (s,
2 H, benzylic CH2), 6.50–7.65 (m, 35 H, ArH
and H-3); FABMS (positive-ion mode, NBA
matrix): m/z 1018 [M+H]+. Anal. Calcd for
C65H60O11: C, 76.75; H, 5.95. Found: C, 76.70;
H, 5.98.
tetra - O - benzyl - i -
droxy-7-methoxy-4
D
- glucopyranosyl) - 5 - hy-
H-1-benzopyran-4-one
(15).—The reaction using a compound 14
(3.18 g, 2.91 mmol), iodine (37 mg, 0.14
mmol, 0.05 equiv), and Me2SO (30 mL), and
the post-treatment and isolation were carried
out in the same manner as described above for
9. Compound 15 was obtained (2.37 g, 81%)
as a colorless amorphous powder: mp 57–
58 °C; [h]2D5 −9° (c 1.0, CHCl3); Rf 0.29 (3:1
hexane–EtOAc); IR (KBr): w 3087, 3062,
3030, 3006, 2935, 2902, 2864, 1653, 1603,
1591, 1512, 1496, 1454, 1439, 1363, 1327,
1292, 1259, 1207, 1171, 1144, 1115, 1066,
1028, 1003, 912, 847, 822, 808, 735, 696 cm−1
;
1H NMR (DMSO-d6 at 140 °C): l 3.61 (dt, 1
H, J5%%,6%% 3.2, J4%%,5%% 9.3 Hz, H-5%%), 3.70 (d, 2 H,
8-C-i- -Glucopyranosyl-2-(3,4-dihydroxy-
D
J5%%,6%% 3.2 Hz, H-6%%a,6%%b), 3.73 (t, 1 H, J3%%,4%%
=
phenyl)-5-hydroxy-7-methoxy-4 H-1-benzopy-
ran-4-one; isoswertiajaponin (17).—The reac-
tion using compound 15 (489 mg), 10% Pd–C
(240 mg), EtOAc (10 mL) and EtOH (50 mL)
were carried out as described above for 11.
Isoswertiajaponin 17 was obtained (225 mg,
quant) as a pale yellowish–green powder: mp
(dec) 217–218 °C, lit.13b 252 °C (dec); [h]2D5
−15° (c 0.50, MeOH); Rf 0.47 (25:35:5:1
Me2CO–EtOAc–water–AcOH); IR (KBr):
J4%%,5%% 9.3 Hz, H-4%%), 3.80 (dd, 1 H, J2%%,3%% 8.5,
J3%%,4%% 9.3 Hz, H-3%%), 3.87 (s, 3 H, ꢀOMe), 4.10
(d, 1 H, Jgem 11.6 Hz, benzylic CH2), 4.19 (br.
t, J 9.2 Hz, H-2%%), 4.40 (d, 1 H, Jgem 11.6 Hz,
benzylic CH2), 4.44 (d, 2 H, Jgem 11.6 Hz,
benzylic CH2), 4.61 (d, 1 H, Jgem 11.4 Hz,
benzylic CH2), 4.75 (d, 1 H, Jgem 11.4 Hz,
benzylic CH2), 4.79 (d, 1 H, Jgem 11.5 Hz,
benzylic CH2), 4.83 (d, 1 H, Jgem 11.5 Hz,